CN108366915A

CN108366915A - The combination of poly ion complexes particle and non-polymeric acid with two or more acid dissociation constants

Info

Publication number: CN108366915A
Application number: CN201680073128.8A
Authority: CN
Inventors: 河西毅彦; 白谷俊史; 浅沼秀彦; R.辛哈; C.杜穆索克斯
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2015-12-15
Filing date: 2016-09-23
Publication date: 2018-08-03
Also published as: US20180369080A1; US11389379B2; KR102425633B1; KR20180083367A; JP2017109936A; KR20210032569A; KR102422887B1; EP3389595A1; WO2017104221A1; KR20210008182A; JP6921476B2; CN116617116A

Abstract

The present invention relates to composition according to the present invention, it includes：(a) at least one particle, the particle include at least one cationic polymer, at least one anionic polymer and at least one non-polymeric acid or its salt with two or more pKa values；(b) at least one physiologically acceptable volatile media.Composition according to the present invention is stablized and can have various cosmetology functions.For example, composition according to the present invention, which can be prepared, such as absorbs or adsorbs the film that stink, the appearance for changing keratin substrate such as skin, the sense of touch for changing keratin substrate and/or protection keratin substrate resist such as dust or pollutant with cosmetic result.

Description

Poly ion complexes particle and with the non-polymeric of two or more acid dissociation constants The combination of acid

Technical field

The present invention relates to the films of composition and poly ion complexes particle including poly ion complexes particle, and use Poly ion complexes particle prepares the method for film and poly ion complexes particle is used to prepare the purposes of film.

Background technology

The poly ion complexes formed with anionic polymer and cationic polymer are known.

Such as WO 2013/153678 and JP-A-2014-227389 is it is also proposed that the film made of poly ion complexes is used for Cosmetic use.Film disclosed in WO 2013/153678 and JP-A-2014-227389 can provide certain cosmetic results.

But the preparation of film disclosed in WO 2013/153678 and JP-A-2014-227389 needs spin-coating method, needs The high speed rotation for wanting substrate, therefore, it is difficult to the film is prepared in situ in keratin substrate such as skin.

JP-A-2015-107939 is disclosed by spraying anionic polymer and cationic polymerization on keratin substances The the first any solution and spraying anionic polymer of object and the second another solution of cationic polymer are to mix Anion and cationic polymer are prepared for cosmetic use with being formed including the film of poly ion complexes by polyion Film made of compound.Film can be prepared in situ on keratin substances such as skin in this preparation.

But it if without carefully controlling, is likely difficult to prepare by spray coating method disclosed in JP-A-2015-107939 Above-mentioned film, because the amount for the first and second solution to be sprayed may be not easily controlled.Particularly, by using JP-A-2015- Spray coating method disclosed in 107939 prepares relatively thick film may be difficult.

One option of easy to manufacture film made of poly ion complexes is the poly ion complexes using particulate forms. It is answered including the polyion formed by anionic polymer and cationic polymer for example, JP-A-2005-36190 is disclosed The dispersion of polymer particle.

Disclosure of the invention

However it has been found that the dispersion including poly ion complexes particle is not all-the-time stable.If the dispersion is unstable Fixed, poly ion complexes particle tends to precipitate.

Therefore, the first purpose of the invention is to provide the stabilization compositions including poly ion complexes particle, such as stablize Dispersion.

The above-mentioned purpose of the present invention can realize that the composition includes by a kind of composition：

(a) at least one particle, it includes

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values；With

(b) at least one physiologically acceptable volatile media.

The charge density of the cationic polymer can be 0.1 meq/g to 20 meq/g, preferably 1 to 15 meq/g, more It is preferred that 4 to 10 meq/g.

The cationic polymer can have at least one selected from secondary or tertiary amino, quaternary ammonium group, guanidine radicals, biguanides base, imidazoles Positively chargeable and/or the positively charged part of base, imino group, pyridyl group and amino.

The cationic polymer can be selected from the cyclopolymer of cyclopolymers of alkyldiallylamine and the ring of dialkyl diallyl ammonium Fluidized polymer, such as (total) polydiene propyl dialkylammonium chloride, (total) polyamine, such as (total) polylysine, cationic (total) poly- ammonia Base acid, such as collagen and its salt.

If the anionic polymer is synthetic anionic polymer, the charge density of the anionic polymer can be 0.1 meq/g to 20 meq/g, preferably 1 to 15 meq/g, more preferable 4 to 10 meq/g, and if the anionic polymer is The average substitution degree of natural anionic polymer, the anionic polymer can be 0.1 to 3.0, preferably 0.2 to 2.7, more preferably 0.3 to 2.5.

The anionic polymer can have at least one selected from sulfate, sulfate radical, sulfonic group, sulfonate radical, phosphate, phosphorus Acid group, phosphonic acid base, phosphonate radical, carboxylic acid group and carboxylate radical part that can be negatively charged and/or negatively charged.

The anionic polymer can be selected from polysaccharide, such as alginic acid, hyaluronic acid and cellulosic polymer（Such as hydroxy ethyl fiber Element, hydroxypropyl cellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethyl cellulose）, anion (total) polyaminoacid Such as (total) polyglutamic acid, (total) poly- (methyl) acrylic acid, (total) polyamic acid, (total) poly styrene sulfonate, (total) poly- (ethylene Sulfate), dextran sulfate, chondroitin sulfate, (total) poly, (total) poly- fumaric acid, maleic anhydride (co) polymer, and Its salt.

The ratio of the amount of cationic polymer/anionic polymer can be 0.05-18, preferably 0.1-10, more preferably 0.5-5.0。

Cationic polymer or anionic polymer or cation and anionic polymerisation in composition according to the present invention The amount of object can be 0.01 to 20 weight % of the composition total weight, preferably 0.1 to 15 weight %, more preferable 0.3 to 12 weight Measure %.

Can be organic acid or its salt, preferably hydrophilic or water with the non-polymeric acid of two or more pKa values or its salt Soluble organic acid or its salt.

Non-polymeric acid with two or more pKa values can be non-polymeric polybasic acids.

Non-polymeric acid with two or more pKa values can be at least two selected from carboxylic acid group, sulfate, sulfonic acid The acidic group of base, phosphonic acid base, phenolic hydroxyl and its mixture.

With the non-polymeric acid of two or more pKa values or its salt can be selected from Terephthalidene Dicamphor Sulfonic Acid and its Salt（Mexoryl SX）、Yellow 6（Sunset Yellow FCF）, ascorbic acid and its salt and its mixture.

Amount with the non-polymeric acid of two or more pKa values or its salt in composition according to the present invention can be 0.001 to 30 weight % of the composition total weight, preferably 0.01 to 20 weight %, more preferable 0.1 to 15 weight %.

(a) size of particle can be 50 nm to 100 μm, preferably 200 nm to 50 μm, more preferable 300 nm to 30 μ m。

(a) amount of the particle in composition according to the present invention can be 0.01 to 60 weight % of the composition total weight, It is preferred that 0.1 to 50 weight %, more preferable 1 to 40 weight %.

(b) at least one physiologically acceptable volatile media（It is preferred that water）Amount in composition according to the present invention Can be 50 to the 99 weight %, preferably 60 to 97 weight %, more preferable 70 to 95 weight % of the composition total weight.

The pH of composition according to the present invention can be 3 to 9, preferably 3.5 to 8.5, more preferable 4 to 8.

Composition according to the present invention can further include (c) at least one oil and be emulsion form.

Composition according to the present invention can further include (d) at least one emulsifier, preferred polymeric emulsifier.

Composition according to the present invention can be cosmetic composition, preferably skin cosmetic composition.

Second object of the present invention be to provide can be easy to prepare it is relatively thick made of poly ion complexes particle The method of film.

The above-mentioned purpose of the present invention can be prepared by a kind of with more than 1 μm, preferably 1.5 μm or bigger, more preferable 2 μ The film of m or the thickness of bigger, preferably the method realization of cosmetics film, the method includes：

In substrate, preferably apply composition according to the present invention in keratin substrate；With

The composition is dried.

Third object of the present invention is to provide relatively thick films made of poly ion complexes particle.

The above-mentioned purpose of the present invention can be realized by following film：

(1) have and be more than 1 μm, preferably 1.5 μm or bigger, the film of the thickness of more preferable 2 μm or bigger, preferably cosmetics Film is prepared by the method included the following steps：

The composition is dried,

Or

(2) have and be more than 1 μm, preferably 1.5 μm or bigger, the film of the thickness of more preferable 2 μm or bigger, preferably cosmetics Film, it includes：

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values.

The invention further relates to keratin substrates, such as the beauty method of skin comprising

Apply composition according to the present invention in keratin substrate；With

The composition is dried to form cosmetics film in keratin substrate.

Thus obtained cosmetics film can tolerate pH 7 or smaller water, and available pH is more than 7, preferably 8 or bigger, more excellent Select the water removing of 9 or bigger.

The invention further relates to compositions according to the present invention to be used in keratin substrate as prepared cosmetics film on skin Purposes, wherein the cosmetics film is resistant to pH 7 or smaller water, and available pH is more than 7, preferably 8 or bigger, and more preferable 9 or more Big water removes.

The preferred forms of the present invention

After hard research, it has been found by the present inventors that by by poly ion complexes particle and with two or more The non-polymeric acid of pKa value or its salt merge, and can provide the stabilization composition including poly ion complexes particle, such as stable dispersion Body.Therefore, composition according to the present invention includes：

(a) at least one particle, it includes

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values；With

(b) at least one physiologically acceptable volatile media.

In addition, it has been found by the present inventors that can provide can be easy to prepare made of poly ion complexes particle relatively The method of thicker film.Therefore, be according to the method for the present invention it is a kind of prepare be more than 1 μm, preferably 1.5 μm or bigger, The film of the thickness of more preferable 2 μm or bigger, the preferably method of cosmetics film, the method includes：

The composition is dried.

In addition, it has been found by the present inventors that relatively thick film made of poly ion complexes particle can be provided.Cause This, film according to the present invention is：

The composition is dried,

Or

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values.

Composition long-time stable according to the present invention simultaneously can be used for by the way that the composition is applied to substrate, preferred angle egg White substrate, it is on more preferable skin and the composition is dry and be easy to prepare poly ion complexes film such as skin and hair.

Poly ion complexes film according to the present invention can have various cosmetology functions.

For example, film according to the present invention itself there can be cosmetic result, such as absorbs or adsorb stink, changes keratin substrate As the appearance of skin, the sense of touch of change keratin substrate and/or protection keratin substrate resist such as dust or pollutant.

If poly ion complexes film includes at least one cosmetic active ingredient, which can have by the cosmetic active The cosmetic result that ingredient provides.For example, if poly ion complexes film includes selected from age resister, anti-sebum agent, deodorant, stops Sweat agent, brightening agent and its mixture at least one cosmetic active ingredient, the film can handle skin aging, absorb skin on Sebum, the smell on control skin, the perspiration on control skin and/or skin whitening.

Film according to the present invention can be transparent and therefore may be not easy to discover, although the film is relatively thick.

In addition, film according to the present invention is water-fast, therefore even if keratin substrate surface due to such as sweat and rainwater and It gets wet, which can also stay on keratin substrate such as skin.

In addition, film according to the present invention can be removed easily from keratin substrate such as skin under alkaline condition.Therefore, Film according to the present invention is difficult to be removed with water, and it can easily be removed with the soap that can provide alkaline condition.

Therefore, if film according to the present invention includes ultraviolet filtering agent, film according to the present invention can express out water-fast（It is anti- Water）And can be lasting UV screen effects, but can easily with can provide alkaline condition soap remove.

Explain composition according to the present invention, method, film etc. in more detailed manner below.

[poly ion complexes particle]

Composition according to the present invention includes (a) at least one particle, is poly ion complexes particle.To (a) particle There is no limit for type.Two or more different types of (a) particles can be applied in combination.Therefore, it is possible to use single type (a) particle or different types of (a) particle combination.

(a) particle includes at least one cationic polymer and at least one anionic polymer.To cation and it is cloudy from There is no limit for the type of sub- polymer.Two or more different types of cationic polymers can be applied in combination.Therefore, may be used To use the combination of the cationic polymer or different types of cationic polymer of single type.Can be applied in combination two kinds or More kinds of different types of anionic polymers.Therefore, it is possible to use the anionic polymer of single type or different types of The combination of anionic polymer.

The amount of cationic polymer/anionic polymer（Such as chemical equivalent）Ratio can be 0.05-18, preferably 0.1-10, more preferable 0.5-5.0.Particularly, the anion base of cation group number/anionic polymer of cationic polymer Group's number can be preferably 0.05-18, more preferable 0.1-10, even more preferably 0.5-5.0.

The size of poly ion complexes particle can be 50 nm to 100 μm, preferably 200 nm to 50 μm, more preferable 300 Nm to 30 μm, even more preferably 1 to 20 μm.The granularity less than 1 μm can be measured by dynamic light scattering method, and can be passed through Light microscope measures the granularity more than 1 μm.This granularity is based on volume diameter.

Amount of the poly ion complexes particle in composition according to the present invention can be the 0.01 of the composition total weight To 60 weight %, preferably 0.1 to 50 weight %, more preferable 1 to 40 weight %.

(cationic polymer)

Cationic polymer has positive charge density.The charge density of the cationic polymer can be 0.1 meq/g to 20 Meq/g, preferably 1 to 15 meq/g, more preferable 4 to 10 meq/g.

The molecular weight of the cationic polymer can be preferably 1,000 or bigger, preferably 10, and 000 or bigger, more preferably 100,000 or bigger, even more preferably 1,000,000 or bigger.

The cationic polymer can have at least one selected from secondary or tertiary amino, quaternary ammonium group, guanidine radicals, biguanides base, imidazoles Positively chargeable and/or the positively charged part of base, imino group, pyridyl group and amino.Term (primary) " amino " refers to herein- NH₂Group.

The cationic polymer can be homopolymer or copolymer.Term " copolymer " is understood to mean by two types The copolymer that obtains of monomer and those of obtained by being more than two kinds of monomer, such as by the three of the acquisition of the monomer of three types Membered copolymer.

The cationic polymer can be selected from natural and synthetic cationic polymers.The non-limiting examples of cationic polymer It is as follows.

(1) derived from propylene acid or methacrylate and amide and include at least one unit homopolymer and copolymerization Object, wherein the unit is selected from the unit of following formula：

Wherein：

R₁And R₂, it can be identical or different, it is selected from hydrogen and includes the alkyl of 1 to 6 carbon atom, such as methyl and ethyl；

R₃, it can be identical or different, it is selected from hydrogen and CH₃；

Symbol A, can be identical or different, is selected from and includes 1 to 6 carbon atom, such as the linear chain or branched chain alkane of 2 to 3 carbon atoms Base and the hydroxyalkyl for including 1 to 4 carbon atom；

R₄、R₅And R₆, it can be identical or different, selected from the alkyl and benzyl for including 1 to 18 carbon atom, at least one implementation Include the alkyl of 1 to 6 carbon atom in scheme；And

X is to be derived from inorganic or organic acid anion, such as methyl sulfate anions and halide ion, such as chlorion and bromine Ion.

The copolymer of (1) class also may include that at least one be derived from can be selected from acrylamide, Methacrylamide, double third Ketone acrylamide, the quilt (C on nitrogen-atoms₁-C₄) low alkyl group substitution acrylamide and Methacrylamide, derived from propylene Acid or the group of methacrylic acid and its ester, vinyl lactam such as vinyl pyrrolidone and caprolactam and second The unit of the comonomer of alkenyl esters.

The example of the copolymer of (1) class includes, but are not limited to：

Acrylamide and with dimethyl suflfate or with the quaternized dimethylaminoethyl methacrylate of dimethyl halide Copolymer,

Such as the acrylamide described in European patent application No. 0 080 976 and methacryloxyethyl trimethyl chlorine Change the copolymer of ammonium,

The copolymer of acrylamide and methacryloxyethyl trimethyl ammonium methyl sulfate,

Such as the quaternized or on-quaternised ethenyl pyrrolidone described in French Patent (FRP) Nos. 2 077 143 and 2 393 573 Ketone/dialkyl aminoalkyl acrylates or methacrylate copolymer,

Dimethylaminoethyl methacrylate/caprolactam/vinyl pyrrolidone terpolymer,

Vinyl pyrrolidone/methacryiamidopropyl dimethylamine copolymer, quartenized vinyl base pyrrolidones/dimethyl Propyl methacrylamide copolymer, and

Crosslinked methacrylic acyloxy (C₁-C₄) three (C of alkyl₁-C₄) alkylammonium salt polymer, such as by quaternized with methyl chloride Dimethylaminoethyl methacrylate homopolymerization or pass through acrylamide with the quaternized methacrylic acid two of methyl chloride Methylamino ethyl ester copolymerization obtain polymer, the homopolymerization or copolymerization after with the undersaturated compound containing olefinic（Such as it is sub- Bisacrylamide）Crosslinking.

(2) cationic cellulose derivative, as described in such as French Patent (FRP) No. 1 492 597 includes quaternary ammonium group The cellulose ether derivative of group, if Union Carbide Corporation companies are with " JR "（JR 400、JR 125、JR 30M）Or " LR "（LR 400、LR 30M）It runs after fame the polymer of sale.These polymer are also defined as in CTFA dictionaries With the quaternary ammonium of the epoxide reactive hydroxyethyl cellulose replaced by front three ammonium group.

(3) cationic cellulose derivative is grafted such as cellulose copolymer and with water soluble quaternary ammonium monomer and is described in example Such as the cellulose derivative in United States Patent (USP) No. 4,131,576, such as use for example selected from methylacryloyl ethyl trimethylammonium, first The hydroxy alkyl cellulose of the salt of base acrylamido propyl trimethylammonium and dimethyldiallylammonium salt grafting, such as methylol are fine Dimension element, hydroxyethyl cellulose and hydroxypropyl cellulose.

Commodity corresponding with these polymer include such as National Starch companies with " Celquat L 200 " With the product of " Celquat H 100 " sale of running after fame.

(4) United States Patent (USP) Nos. 3,589,578 and 4, the non-cellulose base cationic polysaccharide described in 031,307, such as Including the guar gum of cationic trialkyammonium group, cationic hyaluronic acid and glucan hydroxypropyl-trimethyl ammonium chloride.Also may be used Salt is used to use, such as 2, the guar gum of the chloride modification of 3- epoxypropyl trimethylammoniums（Guar hydroxypropyltrimonium chlorine Change ammonium）.

Such product is for example by MEYHALL companies with trade name JAGUAR C13 S, JAGUAR C15, JAGUAR C17 and JAGUAR C162 are sold.

(5) include piperazinyl units and containing optionally being inserted by least one entity selected from oxygen, sulphur, nitrogen, aromatic ring and heterocycle The oxidation of the divalent alkyl of the linear chain or branched chain entered or the polymer of hydroxy alkylidene and these polymer and/or quaternary ammonium Change product.Such polymer for example describes in French Patent (FRP) Nos. 2 162 025 and 2 280 361.

(6) such as water-soluble polyaminoamide made of the polycondensation of acid compound and polyamines；These poly- aminoacyls Amine may be crosslinked with selected from following entity：Epoxyhalopropane（epihalohydrin）；Dicyclic oxide；Dianhydride；Unsaturation two Acid anhydride；Double unsaturation derivatives；Double halohydrins；bisazetidiniums；Double halogen acyl group diamines；Double alkyl halides；By can with selected from double Halohydrin, bisazetidinium, double halogen acyl group diamines, double alkyl halides, epoxyhalopropane, dicyclic oxide and double unsaturations are spread out The oligomer that the reaction of the difunctional compound of the entity reaction of biology generates；Crosslinking agent is with each amine groups of polyaminoamide 0.025 to 0.35 mole of amount uses；These polyaminoamides are optionally alkylated, or if they include at least one tertiary amine official Can, they can be quaternized.Such polymer for example describes in French Patent (FRP) Nos. 2 252 840 and 2 368 508.

(7) the poly- aminoacyl generated with bifunctional agent alkylation with polycarboxylic condensation and then by polyalkylenepolyamines Amine derivative, such as two alkylene triamine polymer of adipic acid/dialkyl amido hydroxyalkyl, wherein alkyl include 1 to 4 carbon original Son, such as methyl, ethyl and propyl, and alkylidene includes 1 to 4 carbon atom, such as ethylidene.Such polymer is for example described in method In state patent No. 1 583 363.In at least one embodiment, these derivatives can be selected from adipic acid/dimethylamino Hydroxypropyl diethylenetriamines polymer.

(8) by the polyalkylenepolyamines comprising two primary amine groups and at least one secondary amine group and selected from diethylene glycol (DEG) The polymer that the reaction of the dicarboxylic acids of radical of saturated aliphatic dicarboxylic acids sour and comprising 3 to 8 carbon atoms obtains.Polyalkylenepolyamines with The molar ratio of dicarboxylic acids can be 0.8:1 to 1.4:1；Resulting polyaminoamide is with epoxychloropropane with 0.5:1 to 1.8:The molar ratio reaction of the secondary amine group of 1 epoxychloropropane/polyaminoamide.Such polymer for example describes special in the U.S. In sharp Nos. 3,227,615 and 2,961,347.

(9) cyclopolymer of the cyclopolymer and dialkyl diallyl ammonium of cyclopolymers of alkyldiallylamine, such as comprising extremely The homopolymer and copolymer of main component of the unit of a few unit selected from formula (Ia) and (Ib) as chain：

Wherein：

K and t, can be identical or different, is equal to 0 or 1, summation k+t is equal to 1；

R₁₂Selected from hydrogen and methyl；

R₁₀And R₁₁, it can be identical or different, include such as 1 to 5 selected from the alkyl comprising 1 to 6 carbon atom, wherein alkyl The hydroxyalkyl of carbon atom and rudimentary (C₁-C₄) amidoalkyl；Or R₁₀And R₁₁It can be with nitrogen-atoms connected to them together shape At heterocyclic group, such as piperidyl and morpholinyl；And

Y' is anion, such as bromide ion, chlorion, acetate, borate, citrate, tartrate anion, bisulfate ion, sulfurous Sour hydrogen radical, sulfate radical and phosphate radical.These polymer for example describe in French Patent (FRP) No. 2 080 759 and its In Certificate of Addition 2 190 406.

In one embodiment, R₁₀And R₁₁, it can be identical or different, selected from the alkyl for including 1 to 4 carbon atom.

The example of such polymer includes, but are not limited to (total) polydiene propyl dialkylammonium chloride, such as CALGON companies With the dimethyl diallyl ammonium chloride homopolymer of " MERQUAT 100 " sale of running after fame（And its low weight average molecular mass is same It is object）With with " MERQUAT 550 " diallyldimethylammonium chloride for sale of running after fame and the copolymer of acrylamide.

Include two ammonium polymer of season of the repetitive unit of at least one formula (II)：

Wherein：

R₁₃、R₁₄、R₁₅And R₁₆, it can be identical or different, selected from aliphatic, the alicyclic or araliphatic for including 1 to 20 carbon atom Group and Lower hydroxy alkyl aliphatic group or R₁₃、R₁₄、R₁₅And R₁₆It can together or individually nitrogen-atoms connected to them Form the second heteroatomic heterocycle or R for optionally including non-nitrogen₁₃、R₁₄、R₁₅And R₁₆, it can be identical or different, selected from by least One selected from nitrile group, ester group, acyl group, amide group ,-CO-O-R₁₇- E groups and-CO-NH-R₁₇The group of-E groups takes The linear chain or branched chain C in generation₁-C₆Alkyl, wherein R₁₇It is alkylidene and E is quaternary ammonium group；

A₁And B₁, it can be identical or different, can be linear chain or branched chain selected from the polymethylene for including 2 to 20 carbon atoms, It is saturated or unsaturated, and its may include being connected in main chain or be inserted into main chain selected from aromatic ring, oxygen, sulphur, sulfoxide radicals, At least the one of sulfone group, disulphide group, amino, alkyl amino, hydroxyl, quaternary ammonium group, urea groups, amide group and ester group A entity, and

X^-It is to be derived from inorganic or organic acid anion；

A₁、R₁₃And R₁₅Piperazine ring can be formed together with two nitrogen-atoms connected to them；

If A₁Selected from linear chain or branched chain, saturated or unsaturated alkylidene or hydroxy alkylidene, B₁It can be selected from：

-(CH₂)_n--CO-E'-OC-(CH₂)_n-

Wherein E' is selected from：

A) diol residue of formula-O-Z-O-, wherein Z are selected from the group of linear chain or branched chain hydrocarbyl group and following formula：

-(CH₂-CH₂-O)_x-CH₂-CH₂-

-[CH₂-CH(CH₃)-O]_y-CH₂-CH(CH₃)-

Wherein x and y, can be identical or different, selected from 1 to 4 integer for representing defined and the unique degree of polymerization and represents flat The numerical value of right 1 to 4 of homopolymerization；

B) double-secondary diamine residue, such as bridged piperazine derivatives；

C) double-primary diamines residue of formula-NH-Y-NH-, wherein Y are selected from linear chain or branched chain hydrocarbyl group or bivalent group-CH₂- CH₂-S-S-CH₂-CH₂-；With

D) urylene of formula-NH-CO-NH-.

In at least one embodiment, X^-It is anion, such as chlorion or bromide ion.

Such as in French Patent (FRP) Nos. 2 320 330；2 270 846；2 316 271；2 336 434 and 2 413 907 With United States Patent (USP) Nos. 2,273,780；2,375,853；2,388,614；2,454,547；3,206,462；2,261,002；2, 271,378；3,874,870；4,001,432；3,929,990；3,966,904；4,005,193；4,025,617；4,025, 627；4,025,653；Such polymer is described in 4,026,945 and 4,027,020.

The non-limiting examples of such polymer include including those of the repetitive unit of at least one formula (III)：

Wherein R₁₃、R₁₄、R₁₅And R₁₆, can be identical or different, selected from including the alkyl and hydroxyalkyl of 1 to 4 carbon atom, n and P, can be identical or different, is 2 to 20 integer, and X^-It is to be derived from inorganic or organic acid anion.

(11) polyquaternary polymers of the unit comprising formula (IV)：

Wherein：

R₁₈、R₁₉、R₂₀And R₂₁, can be identical or different, selected from hydrogen, methyl, ethyl, propyl, beta-hydroxyethyl, β-hydroxypropyl ,- CH₂CH₂(OCH₂CH₂)_pOH groups, wherein p are selected from 0 to 6 integer, and condition is R₁₈、R₁₉、R₂₀And R₂₁It is asynchronously hydrogen,

R and s, can be identical or different, is selected from 1 to 6 integer,

Q is selected from 0 to 34 integer,

X^-It is anion, such as halide ion, and

A is selected from dihalo- group and-CH₂-CH₂-O-CH₂-CH₂-。

Such compound for example describes in European patent application No. 0 122 324.

(12) the season polymer of vinyl pyrrolidone and vinyl imidazole.

Other examples of suitable cationic polymer include but not limited to cationic protein and cationic protein water Product is solved, polyalkylene imine, such as polyethyleneimine include the polymerization of the unit selected from vinylpyridine and vinylpyridine unit Object, the condensation product of polyamine and epoxychloropropane, season poly- urylene（quaternary polyureylenes）Derive with chitin Object.

An embodiment according to the present invention, at least one cationic polymer are selected from the fibre comprising quaternary ammonium group The plain ether derivant of dimension, if UNION CARBIDE CORPORATION companies are with the product of " JR 400 " sale of running after fame, cationic ring Fluidized polymer, such as CALGON companies run after fame the two of sale with MERQUAT 100, MERQUAT 550 and MERQUAT S The homopolymer and copolymer of methyl diallyl ammonium chloride, the guar gum and ethylene being modified with 2,3- glycidyl front three ammonium salts The season polymer of base pyrrolidones and vinyl imidazole（quaternary polymer）.

(13) polyamine

As cationic polymer, (total) polyamine can also be used, can be the homopolymer or copolymer with multiple amino. The amino can be primary, secondary, tertiary or quaternary amino.Amino may be present in the polymer backbone or side group of (total) polyamine（If there is） In.

As the example of (total) polyamine, chitosan, (total) polyallylamine, (total) polyvinylamine, (total) poly- can be mentioned Aniline, (total) polyvinyl imidazol, (total) polymethylacrylic acid dimethylamino ethyl, (total) polyvinylpyridine such as (total) Poly- 1- methyl -2- vinylpyridines, (total) polyimides such as (total) polyethyleneimine, (total) polypyridine such as (total) poly- (season pyridine), (total) poly double-guanidine such as (total) polyaminopropyl biguan-ide, (total) polylysine, (total) poly ornithine, (total) poly arginine, it is (total) gather Histidine, aminoglucan, aminocellulose, amino (total) Pioloform, polyvinyl acetal and its salt.

As (total) polyamine, it is preferable to use (total) polylysine.Polylysine is well known.Polylysine can be led to Cross the natural homopolymer of L-lysine made of bacterial fermentation.For example, polylysine can be commonly used for it is natural anti-in food The epsilon-poly-L-lysine of rotten agent.Polylysine is soluble in polar solvent, such as the polyeletrolyte of water, propylene glycol and glycerine.It is poly- Lysine can be bought in a variety of manners, such as poly- D-Lys and polylysine.Polylysine can be salt and/or solution shape Formula.

(14) polyurethane/cationic base acid

As cationic polymer, polyurethane/cationic base acid can be used, can be have the sun of multiple amino and carboxyl from Sub- homopolymer or copolymer.The amino can be primary, secondary, tertiary or quaternary amino.Amino may be present in polyurethane/cationic base acid Polymer backbone or side group（If there is）In.Carboxyl may be present in the side group of polyurethane/cationic base acid（If there is）In.

As the example of polyurethane/cationic base acid, cationization collagen, cationized gelatin, g., stearyl can be mentioned Base ammonium Hydroxypropyl Hydrolyzed Wheat albumen, cocodimonium hydroxypropyl base hydrolyzed wheat protein, Hydroxyproyl Trimethyl ammonium hydrolyze shellfish Sclerotin, ammonium chloride Hydroxypropyl Hydrolyzed Soy albumen, Hydroxyproyl Trimethyl ammonium hydrolytic soya bean protein, cocoyl two Methyl ammonium Hydroxypropyl Hydrolyzed Soy albumen etc..

The cationic polymer is preferably selected from the cyclopolymer and dialkyl diallyl ammonium of cyclopolymers of alkyldiallylamine Cyclopolymer, such as (total) polylysine, cation are (total) gathers for such as (total) polydiene propyl dialkylammonium chloride, (total) polyamine Amino acid such as cationization collagen and its salt.

Amount of the cationic polymer in composition according to the present invention can be the 0.01 to 20 of the composition total weight Weight %, preferably 0.1 to 15 weight %, more preferable 0.3 to 12 weight %.

(anionic polymer)

Anionic polymer has positive charge density.If the anionic polymer is synthetic anionic polymer, the anion The charge density of polymer can be 0.1 meq/g to 20 meq/g, preferably 1 to 15 meq/g, more preferable 4 to 10 meq/g, And if the anionic polymer is natural anionic polymer, the average substitution degree of the anionic polymer can be 0.1 to 3.0, preferably 0.2 to 2.7, more preferable 0.3 to 2.5.

The molecular weight of the anionic polymer can be preferably 1,000 or bigger, preferably 10, and 000 or bigger, more preferably 100,000 or bigger, even more preferably 1,000,000 or bigger.

The anionic polymer can be homopolymer or copolymer.Term " copolymer " is understood to mean by two types The copolymer that obtains of monomer and those of obtained by being more than two kinds of monomer, such as by the three of the acquisition of the monomer of three types Membered copolymer.

The anionic polymer can be selected from natural and synthetic anionic polymer.

The anionic polymer may include at least one hydrophobic chain.

It may include that the anionic polymer of at least one hydrophobic chain can be by being selected from comprising α, the undersaturated carboxylic acid of β-olefinic The monomer (a) of (monomer a ') and 2- acrylamide-2-methylpro panesulfonic acids (monomer a ") is unsaturated comprising olefinic with non-(a) On-surface-active monomer (b) and/or by comprising α, β-monoene belongs to undersaturated acrylic monomer or comprising monoene category insatiable hunger The isocyanate-monomer of sum with unitary non-ionic amphiphilic component or with primary or secondary fatty amine react generate include olefinic insatiable hunger The copolymerization of the monomer (c) of sum obtains.

Therefore, the anionic polymer at least one hydrophobic chain can be obtained by two kinds of route of synthesis：

By monomer (a ') and (c) or (a '), (b) and (c) or (a ") and (c) or the copolymerization of (a "), (b) and (c)

By by monomer (a ') or by monomer (a ') and (b) or (a ") and (b) copolymer that is formed by unitary nonionic two Close compound or primary or secondary fatty amine are modified（Especially esterification or amidation）.

As 2- acrylamide-2-methylpro panesulfonic acid copolymers, article " Micelle can be especially mentioned formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering – Macromolecules, 2000, Vol. 33, No., 10-3694-3704 " and application EP-A-0 750 899 and EP-A-1 069 172 disclosed in those.

That constitute monomer (a ') includes α, and β-monoene belongs to undersaturated carboxylic acid and can be selected from many acid, in particular selected from acrylic acid, Methacrylic acid, crotonic acid, itaconic acid and maleic acid.It is preferably acrylic or methacrylic acid.

What the copolymer may include not no surfactant properties belongs to undersaturated monomer (b) containing monoene.Preferred monomers are Those of insoluble polymer is generated in their homopolymerizations.They can be selected from such as acrylic acid C₁-C₄Arrcostab and metering system Sour C₁-C₄Arrcostab, such as methyl acrylate, ethyl acrylate, butyl acrylate or corresponding methacrylate.It is particularly excellent The monomer of choosing is methyl acrylate and ethyl acrylate.Available other monomers are such as styrene, vinyltoluene, acetic acid second Enester, acrylonitrile and vinylidene chloride.Non-reacted monomer is preferred, these monomers are that wherein single alkenyl is in polymerization item Those of unique reactive group under part.But the monomer for including the group reacted under the action of heat can be optionally employed, such as Hydroxy-ethyl acrylate.

Monomer (c) such as (a), or includes monoene category insatiable hunger by the way that comprising α, β-monoene belongs to undersaturated acrylic monomer The isocyanate-monomer of sum and unitary non-ionic amphiphilic compound or primary or secondary fatty amine react acquisition.

The unitary non-ionic amphiphilic compound or primary or secondary fatty amine for being used to prepare non-ionic monomer (c) are well known.It should Unitary non-ionic amphiphilic compound is typically the alkoxylate hydrophobic compound of the alkylene oxide comprising the hydrophilic segment for constituting the molecule Object.The hydrophobic compound is usually made of aliphatic alcohol or alkyl phenol, and the carbonaceous of at least six carbon atom is included in the compound Chain constitutes the hydrophobic part of the amphipathic compound.

Preferred unitary non-ionic amphiphilic compound is the compound for having lower formula (V)：

R-(OCH₂CHR’)_m-(OCH₂CH₂)_n-OH (V)

Wherein R is selected from the alkyl comprising 6 to 30 carbon atoms or alkylidene and the alkane with the alkyl comprising 8 to 30 carbon atoms Base aryl, R ', which is selected from, includes the alkyl of 1 to 4 carbon atom, and n is about 1 to 150 average and m is about 0 to 50 to be averaged Number, condition is n big at least as m.

Preferably, in the compound of formula (V), R group is selected from the alkyl comprising 12 to 26 carbon atoms and wherein alkyl It is C₈-C₁₃Alkyl phenyl；R ' group is methyl；M=0 and n=1 to 25.

Preferred primary and secondary fatty amine is made of one or two alkyl chain comprising 6 to 30 carbon atoms.

It is used to form non-ionic ammonia carbamate（urethane）The monomer of monomer (c) can be selected from very changeable chemical combination Object.It can use comprising copolymerizable unsaturation, such as acrylic acid series, metha crylic or the undersaturated any chemical combination of allylic Object.Monomer (c) especially can be by belonging to undersaturated isocyanates comprising monoene, especially such as isocyanic acid α, alpha-alpha-dimethyl-m- isopropyls Alkenyl benzyl ester obtains.

Monomer (c) especially can be selected from oxyethylation（1 to 50 EO）C₆-C₃₀Acrylate, the methacrylate of fatty alcohol Or itaconate, such as -20 methacrylate of stereth, oxyethylation（25 EO）Behenyl methacrylate, ethylene oxide Change（20 EO）Itaconic acid list cetyl, oxyethylation（20 EO）Itaconic acid list stearyl or by polyoxyethylated（25 EO）C₁₂-C₂₄The acrylate and oxyethylation that alcohol is modified（1 to 50 EO）C₆-C₃₀The dimethyl-m-isopropenyl benzyl of fatty alcohol Based isocyanate, especially the dimethyl-m-isopropenyl benzyl isocyanate ester of such as oxyethylation docosyl alcohol.

A specific embodiment according to the present invention, it includes α, β-olefinic insatiable hunger which, which is selected from by (a), The carboxylic acid of sum, (b) non-(a) include the undersaturated on-surface-active monomer of olefinic and (c) non-ionic ammonia carbamate （urethane）Monomer（It is unitary non-ionic amphiphilic compound reacts production with belong to undersaturated isocyanates comprising monoene Object）The acrylic acid series terpolymer of acquisition.

As the anionic polymer for including at least one hydrophobic chain, acrylic acid/ethyl acrylate/propylene can be especially mentioned Acid alkyl ester terpolymer, as Rohm ＆ Haas are run after fame the product that sale is 30% water-borne dispersions with Acusol 823； - 20 methacrylate copolymer of acrylate/stereth, as Rohm ＆ Haas are run after fame with Aculyn 22 production of sale Product；(methyl) acrylic acid/ethyl acrylate/oxyethylation（25 EO）Behenyl methacrylate terpolymer, such as Rohm ＆ Haas is run after fame the product that sale is water-based emulsion with Aculyn 28；Acrylic acid/oxyethylation（20 EO）Itaconic acid list spermaceti Ester copolymer, as National Starch are run after fame the product that sale is 30% water-borne dispersions with Structure 3001；Third Olefin(e) acid/oxyethylation（20 EO）Itaconic acid list stearyl copolymer, if National Starch are with Structure 2001 Sale of running after fame is the product of 30% water-borne dispersions；Acrylate/by polyoxyethylated（25 EO）C₁₂-C₂₄What alcohol was modified Acrylate copolymer, as 3V SA are run after fame with Synthalen W2000 the 30-32% copolymer emulsions of sale；Or metering system The dimethyl-m-isopropenyl benzyl isocyanate ester terpolymer of acid/methyl acrylate/ethoxylated docosyl alcohol, such as document Disclosed in EP-A-0 173 109 for 24% water-borne dispersions and include 40 ethylene oxide groups product.

The anionic polymer can be preferably selected from polysaccharide, such as alginic acid, hyaluronic acid and cellulosic polymer（Such as hydroxyl second Base cellulose, hydroxypropyl cellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethyl cellulose）, anion is (total) to be gathered Amino acid such as (total) polyglutamic acid, (total) poly- (methyl) acrylic acid, (total) polyamic acid, (total) poly styrene sulfonate, (total) Poly- (oxyethylene sulfate), dextran sulfate, chondroitin sulfate, (total) poly, (total) poly- fumaric acid, maleic anhydride are (total) poly- Close object and its salt.

The copolymer-maleic anhydride may include that one or more maleic anhydride comonomers and one or more are selected from second The comonomer of vinyl acetate, vinyl alcohol, vinyl pyrrolidone, alkene and styrene comprising 2 to 20 carbon atoms.

Therefore, " copolymer-maleic anhydride " is understood to mean through one or more maleic anhydride comonomers and one Or it is multiple selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, such as octadecylene of the alkene comprising 2 to 20 carbon atoms, Any polymer that the copolymerization of the comonomer of ethylene, isobutene, diisobutylene or isooctene and styrene obtains, the maleic acid Acid anhydride comonomer optional part or complete hydrolysis.It is preferable to use hydrophilic polymers, that is, have the water dissolution more than or equal to 2 g/l The polymer of degree.

It can it is preferable to use the copolymer that the copolymerization by one or more maleic anhydride units obtains, the wherein maleic acids Acid anhydride unit is hydrolysed form, more preferable alkaline salt forms, such as ammonium, sodium, potassium or lithium salt form.

In the advantageous aspect of the present invention, which can have 0.1 to 1, more preferable 0.4 to 0.9 Maleic anhydride units molar fraction.

The weight-average molar mass of the copolymer-maleic anhydride can be 1,000 to 500,000, preferably 1,000 to 50,000.

The copolymer-maleic anhydride is preferably phenylethylene/maleic anhydride copolymer, and more preferable sodium styrene/maleic anhydride is total Polymers.

It is preferable to use the copolymers of 50/50 ratio of styrene and maleic anhydride.

Such as Cray Valley can be used with the benzene of label SMA1000H 30% ammonium salts in water sold 40% sodium in water that ethylene/maleic anhydride (50/50) copolymer or Cray Valley are sold with label SMA1000HNa Phenylethylene/maleic anhydride (50/50) copolymer of salt form.

Amount of the anionic polymer in composition according to the present invention can be the 0.01 to 20 of the composition total weight Weight %, preferably 0.1 to 15 weight %, more preferable 0.3 to 12 weight %.

(non-polymeric acid with two or more acid dissociation constants)

Composition according to the present invention includes at least one non-polymeric acid with two or more pKa values or its salt, that is, extremely Few a kind of non-polymeric acid or its salt with two or more acid dissociation constants.PKa value（Acid dissociation constant）It is this field skill Art personnel are well known and should be in steady temperature, as measured at 25 DEG C.

There is the non-polymeric acid of two or more pKa values or its salt may include in (a) particle for this.

Term " non-polymeric " refers to that the acid is not obtained by the polymerization of two or more monomers herein.Therefore, this is non-poly- It closes acid and is not equivalent to the acid obtained by the polymerization of two or more monomers, such as polycarboxylic acids.

Molecular weight with the non-polymeric acid of two or more pKa values or its salt is preferably 1000 or smaller, preferably 800 Or smaller, more preferable 600 or smaller.

To the type with the non-polymeric acid of two or more pKa values or its salt, there is no limit.Two can be applied in combination Kind or more different types of non-polymeric acid or its salt with two or more pKa values.Therefore, it is possible to use unitary class Type with the non-polymeric acid of two or more pKa values or its salt or different types of with two or more pKa values The combination of non-polymeric acid or its salt.

Term " salt " refers to by being added to suitable alkali with the non-of two or more pKa values in the present specification The salt formed in polymeric acid, can be by non-polymeric acid and alkali with two or more pKa values according to those skilled in the art The reaction of known method obtains.As salt, metal salt can be mentioned, for example, with alkali metal, such as the salt of Na and Ka, and and alkaline earth Metal, such as the salt and ammonium salt of Mg and Ca.

It can be organic acid or its salt that this, which has the non-polymeric acid of two or more pKa values or its salt, it is preferably hydrophilic or Water-soluble organic acid or its salt.

The non-polymeric acid with two or more pKa values can be at least two selected from carboxylic acid group, sulfate, sulfonic acid The acidic group of base, phosphonic acid base, phenolic hydroxyl and its mixture.

There is the non-polymeric acid of two or more pKa values can be selected from dicarboxylic acids, disulfonic acid and di 2 ethylhexyl phosphonic acid and its mixing for this Object.

There is the non-polymeric acid of two or more pKa values or its salt can be selected from oxalic acid, malonic acid, succinic acid, penta 2 for this Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxalyl Acetic acid, tartaric acid and its salt；Aspartic acid, glutamic acid and its salt；Terephthalidene Dicamphor Sulfonic Acid or its salt (Mexoryl SX), Benzophenone 9；Phytic acid and its salt；Red 2 (Amaranth)、Red 102 (New Coccine)、Yellow 5 (Tartrazine)、Yellow 6 (Sunset Yellow FCF)、Green 3 (Fast Green FCF)、Blue 1 (Brilliant Blue FCF)、Blue 2 (Indigo Carmine)、Red 201 (Lithol Rubine B)、Red 202 (Lithol Rubine BCA)、Red 204 (Lake Red CBA)、Red 206 (Lithol Red CA)、Red 207 (Lithol Red BA)、Red 208 (Lithol Red SR)、Red 219 (Brilliant Lake Red R)、 Red 220 (Deep Maroon)、Red 227 (Fast Acid Magenta)、Yellow 203 (Quinoline Yellow WS)、Green 201 (Alizanine Cyanine Green F)、Green 204 (Pyranine Conc)、 Green 205 (Light Green SF Yellowish)、Blue 203 (Patent Blue CA)、Blue 205 (Alfazurine FG)、Red 401 (Violamine R)、Red 405 (Permanent Re F5R)、Red 502 (Ponceau 3R)、Red 503 (Ponceau R)、Red 504 (Ponceau SX)、Green 401 (Naphtol Green B), Green 402 (Guinea Green B) and Black 401 (Naphtol Blue Black)；It is folic acid, anti-bad Hematic acid, arabo-ascorbic acid and its salt；Cystine and its salt；EDTA and its salt；Glycyrrhizic acid and its salt；And its mixture.

There is the non-polymeric acid of two or more pKa values or its salt to be preferably selected from two camphor sulphur of terephthalylidene for this Acid and its salt（Mexoryl SX）, Yellow 6 (Sunset Yellow FCF), ascorbic acid and its salt and its mixture.

This has amount in composition according to the present invention of non-polymeric acid or its salt of two or more pKa values can be with For 0.001 to 30 weight % of the composition total weight, preferably 0.01 to 20 weight %, more preferable 0.1 to 15 weight %.

[physiologically acceptable volatile media]

Composition according to the present invention includes at least one (b) physiologically acceptable volatile media.

Term " physiologically acceptable " volatile media is intended to mean that especially suitable for applying composition according to the present invention The volatile media being added on keratin substances.

Term " volatility " refers to that (b) physiology acceptable medium can be at such as 25 DEG C of standard atmospheric pressure such as 1 atm and room temperature Evaporation.

The physiology acceptable medium usually adapts to the property for the carrier that composition according to the present invention will be applied to thereon, with And adapt to the packaged form of composition according to the present invention.

(b) physiologically acceptable volatile media may include or mixtures thereof at least one hydrophilic organic solvent, water.

As hydrophilic organic solvent, the single methanol for example containing 2 to 6 carbon atoms can be mentioned, such as ethyl alcohol or isopropanol；Especially It contains 2 to 20 carbon atoms, preferably comprises 2 to 10 carbon atoms, preferably comprises the polyalcohol of 2 to 8 carbon atoms, such as sweet Oil, propylene glycol, butanediol, pentanediol, hexylene glycol, pungent ethylene glycol, dipropylene glycol or diethylene glycol；Glycol ethers（Especially contain 3 to 16 carbon atoms）, such as mono-, two- or tripropylene glycol (C₁-C₄) alkyl ether, mono-, two- or triethylene glycol (C₁-C₄) alkyl ether, and Its mixture.

[cosmetic active ingredient]

Composition according to the present invention may include at least one cosmetic active ingredient.To cosmetic active ingredient, there is no limit. Two or more cosmetic active ingredients can be applied in combination.Therefore, it is possible to use the cosmetic active ingredient of single type Or the combination of different types of cosmetic active ingredient.

In cosmetic active ingredient to be used, ultraviolet filtering agent, antioxidant, detergent, freedom can be mentioned Base scavenger, moisturizer, brightening agent, fatty conditioning agent, anti-acne agents, antidandruff agent, age resister, softening agent, anti wrinkling agent, angle Matter release agent, anti-inflammatory agent, freshener, consolidant, Vasoprotectant, antibacterial agent, antifungal agent, antiperspirant, deodorant, skin Conditioner, anesthetic, immunomodulator, nutritional agents and sebum absorbing agent or moisture absorber.

The non-polymeric acid with two or more pKa values preferably serves as cosmetic active agent.If this has The non-polymeric acid of two or more pKa values may act as cosmetic active agent, and composition according to the present invention can need not include changing Cosmetic activating agent.

Composition according to the present invention may include 0.01 to 50 weight % of the composition total weight, preferably 0.1 to 40 weight %, more preferable 1 to 30 weight % are measured, even more preferably the cosmetic active ingredient of the amount of 2 to 20 weight %.

(ultraviolet filtering agent)

According to a preferred embodiment of the invention, which can be selected from ultraviolet filtering agent.

To the type of the ultraviolet filtering agent there is no limit.The ultraviolet light mistake of two or more types can be applied in combination Filtering agent.Therefore, it is possible to use the combination of the ultraviolet filtering agent of single type or different types of ultraviolet filtering agent.This is ultraviolet Line filtering agent can be selected from inorganic UV filtering agent, organic uv filtering agent and its mixture.

(inorganic UV filtering agent)

Composition according to the present invention may include at least one inorganic UV filtering agent.If inorganic using two or more Ultraviolet filtering agent, they can be identical or different, preferably identical.

Inorganic UV filtering agent for the present invention can be active in the areas UV-A and/or UV-B.The inorganic UV Line filtering agent can be hydrophilic and/or lipophilic.The inorganic UV filtering agent common solvent such as water preferably in cosmetics Be insoluble in ethyl alcohol.

The inorganic UV filtering agent is preferably fine-grained form so that it is average（It is primary）Grain size be 1 nm to 50 nm, it is excellent Select 5 nm to 40 nm, more preferable 10 nm to 30 nm.It is average（It is primary）Granularity is average（It is primary）Grain size is arithmetic average herein Diameter.

The inorganic UV filtering agent can be selected from silicon carbide, possible coating or uncoated metal oxide and its mixing Object.

The inorganic UV filtering agent is preferably selected from the pigment formed by metal oxide（The average-size of primary particle： Usual 5 nm to 50 nm, preferably 10 nm are to 50 nm）, such as by titanium oxide（Amorphous or with rutile and/or anatase form Crystallization）, the pigment that is formed of iron oxide, zinc oxide, zirconium oxide or cerium oxide, they are all UV light protective agents commonly known per se.It should Inorganic UV filtering agent is preferably selected from titanium oxide, zinc oxide, more preferable titanium oxide.

The inorganic UV filtering agent can be coating or uncoated.The inorganic UV filtering agent can have at least one A coating.The coating may include being selected from aluminium oxide, silica, aluminium hydroxide, organosilicon, silane, aliphatic acid or its salt（Such as Sodium, potassium, zinc, iron or aluminium salt）, fatty alcohol, lecithin, amino acid, polysaccharide, protein, alkanolamine, wax such as beeswax, (methyl) third At least one compound of alkene acids polymers, organic uv filtering agent and (complete) fluorine compounds.

The coating preferably includes at least one organic uv filtering agent.As the organic uv filtering in the coating Agent, preferable dibenzoylmethane derivative such as butyl methoxydibenzoylmethise（Avobenzone）With such as BASF conducts 2,2' methylene bis [6- (2H- benzotriazole -2- bases) -4- (1,1,3,3- tetramethyls-butyl) that " TINOSORB M " is sold Phenol]（Methylene bis-benzotriazolyl tetramethyl butyl phenol）.

In a known way, the organosilicon in the coating can be comprising line style or cyclic annular and branched or cross-linked structure, have Variable molecular amount is obtained by the polymerization and/or polycondensation of suitable functional silane and is made of substantially formant repeatedly Organosilicon polymer or oligomer, wherein silicon atom are interconnected through oxygen atom（Siloxanes key）, the alkyl optionally replaced is through carbon Atom is directly connected on the silicon atom.

Term " organosilicon " further includes the silane needed for their preparation, especially alkyl silane.

Organosilicon for the coating is preferably selected from alkyl silane, polydialkysiloxane and polyalkylhydrogensiloxanes. The organosilicon is more preferably selected from octyl trimethyl monosilane, dimethyl silicone polymer and polymethyl hydrogen siloxane.

Certainly, before being handled with organosilicon, the inorganic UV filtering agent made of metal oxide can use it Its surface agent especially uses the processing of or mixtures thereof cerium oxide, aluminium oxide, silica, aluminium compound, silicon compound.

It can be by imposing inorganic UV filtering agent with any compound as described above and polyethylene, metal Alkoxide（Titanium or aluminium-alcohol salt）, metal oxide, calgon and such as Cosmetics ＆ Toiletries, nineteen ninety 2 Month, volume 105, one or many chemistry, electronics, mechanochemistry and/or the engineering properties of those shown in the 53-64 pages Surface treatment prepare the inorganic UV filtering agent of coating.

The inorganic UV filtering agent of the coating can be the titanium oxide coated with llowing group of materials：

With silicon dioxide coating, the product " Sunveil " such as from Ikeda；

With silica and iron oxide-coated, the product " Sunveil F " such as from Ikeda；

With silica and alumina coated, " the Microtitanium Dioxide MT 500 of the product such as from Tayca SA ", from Tioxide's " Tioveil " and from Rhodia's " Mirasun TiW 60 "；

With alumina coated, the product " Tipaque TTO-55 (B) " such as from Ishihara and " Tipaque TTO-55 (A) " and from Kemira's " UVT 14/4 "；

Coated with aluminium oxide and aluminum stearate, the product such as from Tayca " 100 T of Microtitanium Dioxide MT, MT 100 TX, MT 100 Z or MT-01 ", the product from Uniqema " Solaveil CT-10 W " and " Solaveil CT , and the product from Merck " Eusolex T-AVO " 100 "；

It is coated with aluminium oxide and Aluminum trilaurate, the product " 100 S of Microtitanium Dioxide MT " such as from Tayca；

It is coated with iron oxide and ferric stearate, the product " 100 F of Microtitanium Dioxide MT " such as from Tayca；

It is coated with zinc oxide and zinc stearate, the product " BR351 " such as from Tayca；

It is handled with silica and alumina coated and with organosilicon, such as product " the Microtitanium from Tayca 600 SAS of Dioxide MT ", " Microtitanium Dioxide MT 500 SAS " with " Microtitanium Dioxide MT 100 SAS"；

It is coated and is handled with organosilicon, the product such as from Titan Kogyo with silica, aluminium oxide and aluminum stearate " STT-30-DS ",

It is handled with silicon dioxide coating and with organosilicon, the product " UV-Titan X 195 " such as from Kemira；

It handles, product " Tipaque TTO-55 (S) " such as from Ishihara or comes from alumina coated and with organosilicon " the UV Titan M 262 " of Kemira；

It is coated with triethanolamine, the product " STT-65-S " such as from Titan Kogyo；

It is coated with stearic acid, the product " Tipaque TTO-55 (C) " such as from Ishihara；Or

It is coated with calgon, the product " 150 W of Microtitanium Dioxide MT " such as from Tayca.

Octyl trimethyl silane treated and its single-particle are preferably used with other titanium oxide pigments that organosilicon is handled Average-size be 25 to 40 nm TiO₂, as Degussa Silices are sold with trade mark " T 805 "；Use polydimethylsiloxanes The TiO that the average-size of alkane processing and its single-particle is 21 nm₂, such as Cardre is with trade mark " 70250 Cardre UF TiO₂Si₃It " sells；With the anatase/gold handled with polydimethylhydrogensiloxane and the average-size of its single-particle is 25 nm Red stone TiO₂, " the Microtitanium Dioxide USP Grade if Color Techniques are with trade mark Hydrophobic " is sold.

Preferably use following coating TiO₂Inorganic UV filtering agent as coating：

Stearic acid（With）Aluminium hydroxide（With）TiO₂, the product " MT-100 TV " such as from Tayca, average primary particle diameter 15 nm；

Dimethyl silicone polymer（With）Stearic acid（With）Aluminium hydroxide（With）TiO₂, such as product from Miyoshi Kasei " SA-TTO-S4 ", average primary particle diameter are 15 nm；

Silica（With）TiO₂, the product " MT-100 WP " such as from Tayca, average primary particle diameter is 15 nm；

Dimethyl silicone polymer（With）Silica（With）Aluminium hydroxide（With）TiO₂, the product " MT-Y02 " such as from Tayca " MT-Y-110 M3S ", average primary particle diameter are 10 nm；

Dimethyl silicone polymer（With）Aluminium hydroxide（With）TiO₂, the product " SA-TTO-S3 " such as from Miyoshi Kasei, Average primary particle diameter is 15 nm；

Dimethyl silicone polymer（With）Aluminium oxide（With）TiO₂, the product " UV TITAN M170 " such as from Sachtleben, put down Equal primary particle diameter is 15 nm；With

Silica（With）Aluminium hydroxide（With）Alginic acid（With）TiO₂, the product " MT-100 AQ " such as from Tayca, averagely just Grade grain size is 15 nm.

For ultraviolet filtering ability, with the TiO of at least one organic uv filtering agent coating₂More preferably.For example, Avobenzone can be used（With）Stearic acid（With）Aluminium hydroxide（With）TiO₂, the product " HXMT-100ZA " such as from Tayca, Average primary particle diameter is 15 nm.

Uncoated titanium oxide pigments for example by Tayca with trade mark " Microtitanium Dioxide MT500B " or " Microtitanium Dioxide MT600B ", by Degussa with trade mark " P 25 ", by Wacker with trade mark " Oxyde de Titane transparent PW ", by Miyoshi Kasei with trade mark " UFTR ", by Tomen with trade mark " ITS " and by Tioxide is sold with trade mark " Tioveil AQ ".

Uncoated zinc oxide pigment is for example：

Sunsmart is with those of trade mark " Z-cote " sale；

Elementis is with those of trade mark " Nanox " sale；With

Nanophase Technologies are with those of trade mark " Nanogard WCD 2025 " sale.

The zinc oxide pigment of coating is for example：

Toshiba is with those of trade mark " Oxide Zinc CS-5 " sale（The ZnO of polymethyl hydrogen siloxane coating）；

Nanophase Technologies are with those of trade mark " Nanogard Zinc Oxide FN " sale（As Finsolv TN, benzoic acid C₁₂-C₁₅40% dispersion in Arrcostab）；

Daito is with those of trade mark " Daitopersion Zn-30 " and " Daitopersion Zn-50 " sale（In ethylene oxide Change the dispersion in dimethyl silicone polymer/cyclopolymethyl siloxane, including 30% or 50% by silica and poly- methyl hydrogen silicon The nano zine oxide of oxygen alkane coating）；

Daikin is with those of trade mark " NFD Ultrafine ZnO " sale（As point in ring five dimethyl silicone polymer Granular media by the phosphate of perfluoroalkyl and the copolymer based on perfluor alkyl ethide coating ZnO）；

Shin-Etsu is with those of trade mark " SPD-Z1 " sale（It is dispersed in being grafted by organosilicon in cyclomethicone The ZnO of acrylic polymer coating）；

ISP is with those of trade mark " Escalol Z100 " sale（It is total to be dispersed in ethylhexyl methoxy cinnamate/PVP- hexadecylenes The ZnO that alumina treatment in polymers/polymethyl siloxane mixture is crossed）；

Fuji Pigment are with those of trade mark " Fuji ZnO-SMS-10 " sale（By silica and poly- methyl silsesquioxane The ZnO of alkane coating）；With Elementis with those of trade mark " Nanox Gel TN " sale（It is dispersed in benzoic acid C with 55%₁₂- C₁₅Arrcostab and the ZnO in hydroxy stearic acid condensation polymer）.

Uncoated cerium oxide pigment is for example gone out by Rhone-Poulenc with trade mark " Colloidal Cerium Oxide " It sells.

Uncoated iron oxide pigment for example by Arnaud with trade mark " Nanogard WCD 2002 (FE 45B) ", " 45 BL AQ of Nanogard Iron FE ", " Nanogard FE 45R AQ " and " Nanogard WCD 2006 (FE 45R) " Or it is sold with trade mark " TY-220 " by Mitsubishi.

The iron oxide pigment of coating for example by Arnaud with trade mark " Nanogard WCD 2008 (FE 45B FN) ", " 45 BL " of Nanogard WCD 2009 (FE 45B 556) ", " 45 BL 345 of Nanogard FE " and " Nanogard FE Or it is sold with trade mark " Oxyde de fer transparent " by BASF.

The mixture of metal oxide, especially titanium dioxide and ceria, including Ikeda can also be mentioned with quotient Mark " Sunveil A " sell by the titanium dioxide of silicon dioxide coating and by the ceria of silicon dioxide coating etc. weight Mixture, and by the mixture of the titanium dioxide and zinc oxide of the coating of aluminium oxide, silica and organosilicon, such as Kemira The product " M 261 " of sale, or by aluminium oxide, silica and glycerine coating titanium dioxide and zinc oxide mixture, The product " M 211 " sold such as Kemira.

The inorganic UV filtering agent of coating is preferably as can enhance the ultraviolet light mistake of inorganic UV filtering agent Filter effect.In addition, the coating can help to evenly and homogeneously for ultraviolet filtering agent to be dispersed in composition according to the present invention In.

If, can be made of composition according to the present invention according to this using the inorganic UV filtering agent of fine-grained form The film of invention can also have the effect of not providing white appearance but transparent or clear appearance, because of the inorganic UV filtering agent Particulate do not assemble but can be consistent or be uniformly dispersed in the film.It is noted that inorganic UV filtering agent is freely thin Grain is easy aggregation to assign skin white appearance.

(organic uv filtering agent)

Composition according to the present invention may include at least one organic uv filtering agent.If organic using two or more Ultraviolet filtering agent, they can be identical or different, preferably identical.

Organic uv filtering agent for the present invention can be active in the areas UV-A and/or UV-B.The organic ultraviolet Line filtering agent can be hydrophilic and/or lipophilic.

The organic uv filtering agent can be solid or liquid.Term " solid " and " liquid " refer at 25 DEG C and 1 It is solid and liquid respectively under atm.

The organic uv filtering agent can be selected from o-amino benzoyl acid compound；Dibenzoylmethane compounds；Cinnamic acid Compound；Salicylic acid compound；Naphthalene compound；Benzophenone cpd；β, β-diphenylacrylate ester compounds；Triazine Close object；Benzotriazole cpd；Toluenyl malonic ester compound；Benzimidazole compound；Imidazolinium compounds；Double-benzo Oxazolyl compound；P-aminobenzoic acid（PABA）Compound；Di-2-ethylhexylphosphine oxide (hydroxy-phenyl benzotriazole) compound；Benzoxazole Close object；Shading（screening）Polymer and shading organosilicon；Dimer derived from alpha-alkyl phenylethylene；4,4- diaryl Adiene cpd；Guaiazulene（guaiazulene）And its derivative；Rutin sophorin and its derivative；And its mixture.

As the example of the organic uv filtering agent, can mention the INCI names below with them those of point out and its Mixture.

O-amino benzoyl acid compound:Haarmann and Reimer are sold with trade mark " Neo Heliopan MA " Menthyl anthranilate.

Dibenzoylmethane compounds:What Hoffmann-La Roche were especially sold with trade mark " Parsol 1789 " Butyl methoxydibenzoylmethise；With isopropyl dibenzoyl methane.

Cinnamic acid compounds:The methoxyl group meat that Hoffmann-La Roche are especially sold with trade mark " Parsol MCX " Cinnamic acid ethylhexyl；Methoxycinnamate isopropyl propionate；Methoxy cinnamic acid isopropyl oxygen ester；Haarmann and Reimer are with quotient Mark the methoxycinnamate isoamyl valerate that " Neo Heliopan E 1000 " is sold；Cinoxate（4- methoxy cinnamic acid 2- ethoxies Base ethyl ester）；Methoxy cinnamic acid DEA salt；Methyl cinnamic acid diisopropyl ester；With glyceryl ethylhexanoate ester dimethoxy-cinnamic acid Ester.

Salicylic acid compound:The Homosalate that Rona/EM Industries are sold with trade mark " Eusolex HMS " （homomentyl salicylate）；The bigcatkin willow that Haarmann and Reimer are sold with trade mark " Neo Heliopan OS " Sour ethylhexyl；Glycol salicylate；Bigcatkin willow acid butyl monooctyl ester；Phenyl salicylate；Scher is sold with trade mark " Dipsal " Dipropylene glycol salicylate；The TEA salicylic acids sold with trade mark " Neo Heliopan TS " with Haarmann and Reimer Salt.

Naphthalene compound, especially benzylidene camphor derivative：The 3- that Chimex is manufactured with trade mark " Mexoryl SD " Benzylidene camphor；The 4 methyl benzylidene camphor that Merck is sold with trade mark " Eusolex 6300 "；Chimex is with trade mark The benzylidene camphor sulfonic acid of " Mexoryl SL " manufacture；Chimex pricks ammonium methyl with the camphor benzene that trade mark " Mexoryl SO " manufactures Sulfate；The Terephthalidene Dicamphor Sulfonic Acid that Chimex is manufactured with trade mark " Mexoryl SX "；With Chimex with trade mark The polyacrylamide base methyl benzylidene camphor of " Mexoryl SW " manufacture.

Benzophenone cpd:The benzophenone-1 that BASF is sold with trade mark " Uvinul 400 "（2,4- dihydroxy two Benzophenone）；The benzophenone-2 that BASF is sold with trade mark " Uvinul D50 "（Tetrahydroxybenzophenone）；BASF is with trade mark The benzophenone-3 that " Uvinul M40 " is sold（ESCALOL 567）Or Oxybenzone；BASF is with trade mark The UVINUL MS 40 that " Uvinul MS40 " is sold（Group oxybenzone sulfonic acid）；Benzophenone -5（Hydroxymethoxy two Benzophenone sodium sulfonate）；The benzophenone -6 that Norquay is sold with trade mark " Helisorb 11 "（Dihydroxy dimethoxy hexichol first Ketone）；The benzophenone -8 that American Cyanamid are sold with trade mark " Spectra-Sorb UV-24 "；BASF is with trade mark The Benzophenone 9 that " Uvinul DS-49 " is sold（Dihydroxy dimethoxy-benzophenone disulfonate）；Benzophenone-1 2 With 2- (4- diethylamino -2- hydroxy benzoyls) the just own ester of benzoic acid（The UVINUL A+ of BASF）.

- β, β-diphenylacrylate ester compounds:The Losec that BASF is especially sold with trade mark " Uvinul N539 " is vertical Woods；The etocrilene especially sold with trade mark " Uvinul N35 " with BASF.

Triaizine compounds:The diethylhexyl butamido triazine that Sigma 3V are sold with trade mark " Uvasorb HEB " Ketone；2,4,6- tri- (two peopentyl ester of 4'- amino benzal malonic acid)-s- triazines, CIBA GEIGY are with trade mark TINOSORB S The ethylhexyl three that the double-ethyl hexyl oxy phenol methoxyphenyl triazine and BASF sold are sold with trade mark UVINUL T150 Piperazine ketone.

Benzotriazole cpd, especially phenyl benzotriazole derivatives:Branched and linear 2- (2H- benzos three Azoles -2- bases) -6- dodecyl -4- sylvans；With those of described in USP 5240975.

Toluenyl malonic ester compound:4 '-benzylidene malonic acid, two peopentyl ester and include benzal the third two The polysiloxane of acid ester functionality, as Hoffmann-LaRoche is sold with trade mark " Parsol SLX " polysilicone-15。

Benzimidazole compound, especially phenylbenzimidazol derivative：Merck is especially with trade mark " Eusolex What the 232 " Phenylbenzimidazolesulfonic acids sold and Haarmann and Reimer were sold with trade mark " Neo Heliopan AP " Neo Heliopan AP.

Imidazolinium compounds:Dimethoxybenzylidenegroup group dioxoimidazolidin propionic acid ethylhexyl.

Double-benzoxazolyl stilbenes:Derivative as described in EP-669,323 and United States Patent (USP) No. 2,463,264 Object.

P-aminobenzoic acid compound: PABA（P-aminobenzoic acid）, ethylaminobenzoate, dihydroxypropyl pair The dimethyl that benzocaine, amyl dimethyl paraaminobenzoic acid, ISP are especially sold with trade mark " Escalol 507 " The PEG-25 that p-aminobenzoic acid ethylhexyl, p-aminobenzoic acid glyceride and BASF are sold with trade mark " Uvinul P25 " PABA。

Di-2-ethylhexylphosphine oxide-(hydroxy-phenyl benzotriazole) compound, if Fairmount Chemical are in solid form with quotient Mark that 2,2 '-di-2-ethylhexylphosphine oxides [6- (2H- benzotriazole -2- bases) -4- methyl-phenol] that " Mixxim BB/200 " sell, BASF is with quotient " Tinosorb M " or Fairmount Chemical are marked with trade mark " Mixxim BB/100 " with the micronizing in aqueous dispersion 2, the 2 '-di-2-ethylhexylphosphine oxides [6- (2H- benzotriazole -2- bases) -4- (1,1,3,3- tetramethyl butyl) phenol] that form is sold, and such as U.S. State patent Nos. 5,237,071,5,166,355, described in GB-2,303,549, DE-197,26,184 and EP-893,119 Derivative, and

Rhodia Chimie as follows are sold with trade mark " Silatrizole " or L ' Oreal with trade mark " Mexoryl XL " Ethylhexysalicylate：

。

Benzoazole compounds:Sigma 3V are with the bis- [5-1 (dimethyl propylenes of 2,4- that trade mark Uvasorb K2A are sold Base) benzoxazole -2- bases-(4- phenyl) imino group] -6- (2- ethylhexyls) imino group -1,3,5- triazines.

Shading polymer and shading organosilicon:Organosilicon described in WO 93/04665.

It is derived from the dimer of alpha-alkyl phenylethylene:Dimer described in DE-19855649.

- 4,4- diaryl adiene cpds:1,1- dicarboxyls (2,2'- dimethyl propyls) -4,4- diphenyl fourth two Alkene.

The organic uv filtering agent is preferably selected from：

Butyl methoxydibenzoylmethise, ethylhexyl methoxy cinnamate, Homosalate, ethylhexyl salicylate, Losec Vertical woods, Phenylbenzimidazolesulfonic acid, benzophenone-3, UVINUL MS 40, benzophenone -5,2- (4- diethylamino -2- hydroxyls Benzoyl) the just own ester of benzoic acid, bis- [1- [2- [4- (the diethylamino) -2- (2-hydroxybenzoyl)s of 1,1'- (1,4- piperazines diyl) Base] phenyl]-ketone, 4 methyl benzylidene camphor, Terephthalidene Dicamphor Sulfonic Acid, phenyl dibenzimidazole tetrasulfonic acid two Sodium, Uvinul T 150, double-ethyl hexyl oxy phenol methoxyphenyl triazine, Uvasorb HEB, 2,4, 6- tri- (two peopentyl ester of 4'- amino benzal malonic acid)-s- triazines, (two isobutyls of 4'- amino benzal malonic acid of 2,4,6- tri- Ester)-s- triazines, 2,4- be bis--(4 '-amino benzal malonic acid N-butyl) -6- [(3- { 1,3,3,3- tetramethyl -1- [(front threes Base siloxy) disiloxanyl] propyl amino)-s- triazines, 2,4,6- tri--(two-phenyl)-triazine, 2,4,6- tri--(three Biphenyl)-triazine, methylene bis-benzotriazolyl tetramethyl butyl phenol, Ethylhexysalicylate, polysilicone-15, 4 '-benzylidene malonic acid, two peopentyl ester, 1,1- dicarboxyls (2,2'- dimethyl propyls) -4,4- diphenyl diethylenes, 2, Bis- [5-1 (dimethyl propyl) benzoxazole -2- bases-(4- phenyl) imino group] -6- (2- ethylhexyls) imino group -1,3,5- of 4- Triazine, camphor benzene prick ammonium methyl sulphate and its mixture.

The ultraviolet filtering agent can be water-soluble or water dispersible, especially water-soluble.As water soluble ultraviolet The example of line filtering agent can mention Mexoryl SX.In general, the water solubility or water dispersible ultraviolet filtering agent can be by water such as Sweat and rainwater are removed from the surface of keratin substrate such as skin.But due to the water solubility or water dispersible ultraviolet filtering Agent is included in can be by film according to the present invention prepared by composition according to the present invention, the water solubility or water dispersible ultraviolet light Filtering agent is difficult to be removed from film by water, therefore brings lasting UV shield effectiveness.

(brightening agent)

According to a preferred embodiment of the invention, cosmetic active ingredient can be selected from brightening agent.

To the type of brightening agent there is no limit.The brightening agent of two or more types can be applied in combination.It therefore, can be with Use the combination of the brightening agent or different types of brightening agent of single type.

As the example of brightening agent, can mention ascorbic acid or derivatives thereof, kojic acid or derivatives thereof, tranexamic acid or Its derivative, resorcinol or derivatives thereof, alkoxy salicylic acid or its salt, adenosine phosphate or its salt, quinhydrones or its glucosides or Its derivative, glutathione, 4- (4- hydroxyphenyls) -2- butanol, magnolignan（5,5 '-dipropyl-biphenyl -2,2 '-glycol）、 Intacellin, chamomile（chamomilla recutita）Deng.

Ascorbic acid has D-form or L- configurations, and it is preferable to use L- configuration ascorbic acid.Ascorbic acid is also referred to as Vitamin C, and have the function of inhibition melanin production due to the strong reducing action of ascorbic acid.The derivative of ascorbic acid Object can be the salt of ascorbic acid, and the salt of ascorbic acid is preferably selected from sodium ascorbate, magnesium ascorbyl phosphate and anti-bad Hematic acid sodium phosphate.The derivative of ascorbic acid can be the glucosides of ascorbic acid or the ester of ascorbic acid.As ascorbic acid Glucosides example, such as ascorbic acid glucoside can be mentioned.The example of ester as ascorbic acid can be mentioned for example anti- Bad hematic acid silyl ester, tocopherol ascorbate and ascorbic acid alkyl esters.As ascorbic acid alkyl esters, it is preferable to use Ascorbic acid methyl esters or ascorbic acid ethyl ester.Ascorbic acid glucoside is particularly preferred.Ascorbic acid or derivatives thereof can be alone It is applied in combination using or with its two or more type.

As the detailed example of ascorbic acid derivates, it can mention and for example can be used as PRO-AA purchased from Exsymol SAM Bis--O- dimetylsilyl esters of ascorbic acid 5,6-；It can be used as SEPIVITAL EPC and be purchased from Senju Dl- alpha-tocopherol -2-l- the ascorbic acid phosphoric acid esters of Pharmaceutical Co., Ltd.；Stay-C 50 is can be used as to be purchased from The Sodium Ascorbyl Phosphate of Roche；It is purchased from the ascorbic acid Portugal of Hayashibara Biochemical Labs., Inc. Glucosides；3-O- ethylascorbyls；Deng.

Ascorbic acid or derivatives thereof is preferably used with the copolymer in combination of styrene and maleic anhydride.Particularly, above-mentioned At least one portion selective hydrolysis of the maleic anhydride units of copolymer.Above-mentioned hydrolyzed maleic anhydride unit can be basic salt, Such as sodium salt, sylvite, lithium salts form.Above-mentioned maleic anhydride units preferably take up 0.4 to 0.9 mole/1 mole total copolymer, and The ratio of maleic anhydride units and styrene units is preferably 50:50.Particularly, the ratio of maleic anhydride units and styrene units Rate is preferably 50:50, and it is preferable to use ammonium salt or sodium salts.By using ascorbic acid or its derivative with above-mentioned copolymer in combination Object improves the stability of ascorbic acid or derivatives thereof.As above-mentioned copolymer, it is, for example, possible to use can be with production number SMA Styrene/horse of ammonium salts with 30% concentration in water of 1000 H (trade mark) purchased from Atofina Chemicals Inc. Carry out acid anhydride copolymer (50/50)；Or Atofina Chemicals can be purchased from 1000 H Na (trade mark) of production number SMA Inc. the phenylethylene/maleic anhydride copolymer (50/50) of the sodium-salt form with 40% concentration in water.For topical use, on Copolymer is stated with 0.1 to 20 weight % of brightening agent total weight, the concentration of preferably 0.1 to 10 weight % uses.

As an example of derivative of kojic acid, such as kojic acid glycoside can be mentioned.

As the example of tranexamic acid derivative, the dimer of tranexamic acid can be mentioned（As the trans- -4- of hydrochloric acid (it is trans- - Aminomethyl cyclohexane carbonyl) aminomethyl cyclohexane formic acid）, tranexamic acid and quinhydrones ester（Such as trans-4-amino methyl ring Hexane formic acid 4 '-oxybenzene ester）, tranexamic acid and gentianic acid ester（Such as 2- (trans-4-amino hexahydrotoluene carbonyloxy group) -5- Hydroxybenzoic acid and its salt）, ammonia first cyclic amides（As trans-4-amino cyclohexanecarboxylic acid methyl nitrosourea and its salt, it is trans-- 4- (p- methoxybenzoyls base) aminomethyl cyclohexane formic acid and its salt and trans- -4- guanidinomethies naphthenic acid and its Salt）Deng.

As the example of resorcinol derivatives, such as Lucin can be mentioned（Rucinol）Deng.

Alkoxy salicylic acid is that any hydrogen atom wherein in 3- salicylic, 4- or 5- is substituted by alkoxy Compound.Above-mentioned alkoxy is preferably any of methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy and isobutoxy Kind, more preferably methoxy or ethoxy.As the example of the compound, such as 3- methoxysalicylic acids, 3- second can be mentioned Oxygroup salicylic acid, 4- methoxysalicylic acids, 4- ethyoxyls salicylic acid, 4- propoxyl group salicylic acid, 4- isopropoxies salicylic acid, 4- fourths Oxygroup salicylic acid, 5- methoxysalicylic acids, 5- ethyoxyls salicylic acid, 5- propoxyl group salicylic acids etc..The salicylic salt of alkoxy is not It is particularly limited.As the example, such as alkali metal salt or alkali salt, such as sodium salt, sylvite, calcium salt, ammonium can be mentioned Salt, amino-acid salt etc..The sylvite of 4- methoxysalicylic acids is preferred.

As adenosine phosphate or the example of its salt, can mention such as adenosine phosphate disodium.

The example of glucosides as quinhydrones can mention such as hexose glucosides, such as quinhydrones alpha-D-glucose, the Portugals quinhydrones β-D- Grape sugar, quinhydrones α-L- glucose, quinhydrones β-L- glucose, quinhydrones α-D- galactolipins, quinhydrones β-D- galactolipins, quinhydrones α-L- galas Sugar, quinhydrones β-L- galactolipins etc.；Pentose glucosides, such as quinhydrones α-D-ribose, quinhydrones β-D-ribose, quinhydrones α-L- ribose, quinhydrones β- L- ribose, quinhydrones α-D-arabinose, quinhydrones β-D-arabinose, quinhydrones α-L-arabinose, quinhydrones β-L-arabinose etc.； Amino sugar glucosides, such as quinhydrones α-d-glucosamine, quinhydrones β-d-glucosamine, quinhydrones α-L- aminoglucoses, quinhydrones β-L- aminoglucoses, quinhydrones α-D-galactosamine, quinhydrones β-D-galactosamine, quinhydrones α-L- galactosamines, quinhydrones β-L- galactosamines etc.；Urocanic acid glucosides, Such as quinhydrones α-D- glucuronic acids, quinhydrones β-D- glucuronic acids, quinhydrones α-L- glucuronic acids, quinhydrones β-L- glucuronic acids, quinhydrones α- D- galacturonic acids, quinhydrones β-D- galacturonic acids, quinhydrones α-L- galacturonic acids, quinhydrones β-L- galacturonic acids etc.；Etc.. In these compounds, quinhydrones β-D-Glucose（Hereinafter referred to as " ursin "）It is preferred.As spreading out for quinhydrones or its glucosides The example of biology, can mention the salt of such as quinhydrones or its glucosides.Particularly as the example of black bearberry glycoside derivates, Ke Yiti To such as 6-O- caffeoyls ursin etc..

As whitening ingredient, particularly, L-AA or derivatives thereof, kojic acid or derivatives thereof, tranexamic acid Or derivatives thereof, ursin or derivatives thereof and Rucinol be preferred, and ascorbic acid derivates, as 3-O- ethyls L- is anti- Bad hematic acid and L-AA glucoside are more preferable.

[pH]

The pH of the composition can be adjusted by adding at least one alkaline agent and/or at least one acid.It can also pass through At least one buffer is added to adjust the pH of the composition.

(alkaline agent)

Composition according to the present invention may include at least one alkaline agent.Two or more alkaline agents can be applied in combination.Therefore, may be used To use the combination of the alkaline agent or different types of alkaline agent of single type.

The alkaline agent can be inorganic alkaline agent.The inorganic alkaline agent is preferably selected from ammonia；Alkali metal hydroxide；Alkaline-earth metal hydrogen-oxygen Compound；Alkali metal phosphate and dibasic alkaliine, such as sodium phosphate or disodium-hydrogen.

As the example of inorganic alkali hydroxide, sodium hydroxide and potassium hydroxide can be mentioned.As alkaline-earth metal The example of hydroxide can mention calcium hydroxide and magnesium hydroxide.As inorganic alkaline agent, sodium hydroxide is preferred.

The alkaline agent can be organic alkaline agent.Organic alkaline agent is preferably selected from monoamine and its derivative；Diamines and its derivative；It is more Amine and its derivative；Basic amino acid and its derivative；The oligomer and its derivative of basic amino acid；Basic amino acid gathers Close object and its derivative；Urea and its derivative；With guanidine and its derivative.

As the example of organic alkaline agent, alkanolamine can be mentioned, such as mono-, two- and three-ethanol amines and isopropanolamine；Urea, Guanidine and its derivative；Basic amino acid, such as lysine, ornithine or arginine；And diamines, that as described in having structure A bit：

Wherein R refers to optionally by hydroxyl or C₁-C₄Alkyl-substituted alkylidene, such as propylidene, and R₁、R₂、R₃And R₄It is independently Refer to hydrogen atom, alkyl or C₁-C₄Hydroxyalkyl, can be with 1,3- propane diamine and its derivative for.Arginine, urea and monoethanolamine It is preferred.

According to their solubility, alkaline agent can be with 0.1 to 20 weight % of the composition total weight, preferably 0.2 to 10 weight % is measured, the total amount of more preferable 0.3 to 5 weight % uses.

(acid)

Composition according to the present invention may include at least one acid.Two or more acid can be used in combination.Therefore, can make With the combination of the sour or different types of acid of single type.

As acid, common any inorganic or organic acid in cosmetics can be mentioned.Monobasic acid and/or multivalence can be used Acid.Monobasic acid can be used, such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid（HCl）.HCl is preferred.

According to their solubility, acid can be with 0.1 to 15 weight % of the composition total weight, preferably 0.2 to 10 weight % is measured, the total amount of more preferable 0.3 to 5 weight % uses.

(buffer)

Composition according to the present invention may include at least one buffer.Two or more buffers can be applied in combination.Cause This, can use the combination of the buffer or different types of buffer of single type.

As buffer, acetate buffer can be mentioned（Such as acetic acid+sodium acetate）, phosphate buffer（Such as Sodium dihydrogen phosphate+disodium hydrogen phosphate）, citrate buffer agent（Such as citric acid+sodium citrate）, borate buffer （Such as boric acid+Boratex）, tartarate buffer（Such as tartaric acid+two is hydrated sodium tartrate）, Tris buffers（Example Such as three (methylol) aminomethanes）, Hepes buffers（4- (2- ethoxys) -1- piperazine ethanesulfonic acids）.

[optional additives]

Composition according to the present invention can be additionally included in common in the range of not damaging effect of the invention in addition to the above components In the component of cosmetics, especially such as dyestuff, powder, surfactant or emulsifier, oil, thickener, organic non-volatile solvent, Organosilicon and organosilicon derivates, the natural extract derived from animal or plant, wax etc..

Composition according to the present invention may include 0.01 to 50 weight % of the composition total weight, preferably 0.05 to 30 weight Measure %, the above-mentioned optional additives of the amount of more preferable 0.1 to 10 weight %.

In one embodiment, composition according to the present invention may include (c) at least one oil.It can be applied in combination Two or more oil.Therefore, it is possible to use the combination of the oily or different types of oil of single type.Here, term " oil " quilt It is understood as referring to the fatty material for liquid under environment temperature (25 DEG C).

(c) oil can be volatility or non-volatile.

The oil can be animal, plant, mineral or synthesis source.

Term " fixed oil " refers to staying in the oil on keratin substances under room temperature (25 DEG C) and atmospheric pressure.More specifically Ground, fixed oil have strictly less than 0.01 mg/cm²The evaporation rate of/min.

In order to measure this evaporation rate, 15 grams of oil or oil mixture to be tested are placed in the crystallising dish of 7 centimetres of diameter In, which is placed at temperature and is adjusted in 25 DEG C and humidity regulation in about 0.3 cubic metre of big room of 50% relative humidity In balance on.Liquid is allowed freely to evaporate, not agitated liquid, while by being vertically arranged in containing the oily or described mixture Crystallising dish above fan（Papst-Motoren, 8550 N of label are rotated with 2700 rpm）Ventilation, blade direction are provided Crystallising dish, 20 centimetres away from crystallising dish bottom.Periodic measurement stays in the quality of the oil in crystallising dish.Evaporation rate is with per unit area （Square centimeter）Per unit time（Minute）The milligram number of the oil of evaporation indicates.

Term " volatile oil " refers to can be small less than 1 when with skin or lip contact under room temperature (25 DEG C) and atmospheric pressure When interior evaporation any non-aqueous media.Volatile oil is the cosmetics volatile oil for liquid under room temperature (25 DEG C).More specifically, waving Hair oil has 0.01 to 200 mg/cm²The evaporation rate of/min, including boundary.

(volatile oil)

The volatile oil can be selected from the alkyl oil containing 8 to 16 carbon atoms, especially C₈-C₁₆Branched paraffin（Also referred to as different alkane Hydrocarbon）, such as Permethyl 99A（Also referred to as 2,2,4,4,6- five methylheptanes）, isodecane and isohexadecane, such as with trade name Isopar^®Or Permethyl^®The oil of sale.

Also workable volatile oil includes volatile organosilicon, such as linear or ring shape silicone oil, is especially had Have and is less than or equal to 8 centistokes（cSt）（8 × 10^-6 m²/s）Viscosity, especially contain 2 to 10 silicon atoms, especially 2 to 7 Those of a silicon atom, these organosilicons optionally include alkyl or alkoxy containing 1 to 10 carbon atom.As can be used for this The volatile silicone oil of invention, can especially mention viscosity be the dimethyl silicone polymer of 5 and 6 cSt, octamethylcy-clotetrasiloxane, Decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, seven methylhexyl trisiloxanes, seven Methyl Octyl trisiloxanes, six Tetramethyldisiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane and ten dimethyl, five siloxanes and its mixture.

According to an embodiment, cosmetic composition according to the present invention may include the 1 to 80 of the composition total weight Weight % or even 5 to 70 weight % or even 10 to 60 weight %, the especially volatile oil of 15 to 50 weight %.

(fixed oil)

Fixed oil especially can be selected from non-volatile alkyl oil, fluorocarbon oil and/or silicone oil.

The non-volatile alkyl oil that can especially mention includes：

The alkyl oil of animal origin, such as perhydro squalene,

The alkyl oil of plant origin, such as phytostearyl esters, as phytostearyl oleates, phytostearyl are different hard Resin acid ester and lauroyl/octyldodecyl/phytostearyl glutamates（Ajinomoto, Eldew PS203）, by sweet The triglycerides that the aliphatic ester of oil is formed, particularly wherein aliphatic acid can have C₄To C₃₆, especially C₁₈To C₃₆Chain length, These oil can be linear chain or branched chain and saturated or unsaturated；These oil especially can be enanthic acid or Trivent OCG, Shea butter, alfalfa oil, poppy seed oil, winter squash oil, millet oil, big wheat oil, quinoa oil, rye-seed oil, bankoul nut oil, passionflower Oil, sher butter, aloe, Sweet Almond Oil, persic oil（peach stone oil）, peanut oil, argan oil, avocado Oil, kopok oil, borage oil, broccoli oil, pot marigold oil, cameline oil, Canola oil, carrot oil, safflower oil, linseed oil, It is rapeseed oil, cottonseed oil, coconut oil, marrow seed oil, wheat-germ oil, SIMMONDSIA CHINENSIS SEED OIL, lily oil, macadimia nut oil, corn oil, white Awns flower seed oil, St. john's wort oil（St John's Wort oil）, monoi oil, hazelnut oil, apricot kernel oil, nut oil, olive oil, Evening primrose oil, palm oil, blackcurrant seed oil, Chinese gooseberry seed oil, grape seed oil, pistachio oil, winter squash oil, pumpkin seed oil, musk deer Fragrant attar of rose, sesame oil, soybean oil, sunflower oil, castor oil and watermelon seed oil and its mixture or caprylic/capric triglyceride, If those of Stearineries Dubois companies sale or Dynamit Nobel companies are with Miglyol 810,812 and 818 run after fame sale those of,

The linear chain or branched chain hydrocarbon of mineral or synthesis source, such as liquid paraffin and its derivant, vaseline, poly decene, polybutene, hydrogen Change polyisobutene, such as Parleam or saualane；

Synthesis ether containing 10 to 40 carbon atoms；

Synthetic ester, such as formula R₁COOR₂Oil, wherein R₁It is residual to represent the linear chain or branched chain aliphatic acid containing 1 to 40 carbon atom Base and R₂The hydrocarbyl chain of the especially branch containing 1 to 40 carbon atom is represented, condition is chain R₁And R₂In carbon atom number summation More than or equal to 10.The ester especially can be selected from the aliphatic ester of alcohol, such as cetearyl stearyl ester, isopropyl alcohol ester, such as nutmeg Isopropyl propionate, isopropyl palmitate, ethyl palmitate, palmitic acid 2- ethylhexyls, isopropyl stearate, isostearic acid isopropyl Ester, isostearic acid iso stearyl ester, octyl stearate, hydroxylating ester, for example, lactic acid iso stearyl ester, octyl hydroxystearate, Diisopropyl adipate, heptanoate, especially enanthic acid iso stearyl ester, alcohol or polyol caprylate, decylate or ricinoleate, Such as propylene, Octanoic acid, hexadecyl ester, sad tridecane base ester, bis- enanthic acid 2- ethylhexyls of 4-, palmitic acid 2- ethyls Own ester, benzoic acid alkyl base ester, two heptanoate of polyethylene glycol, propylene glycol 2- ethylhexanoates and its mixture, C₁₂-C₁₅Alcohol benzene Formic acid esters, lauric acid hexyl ester, pivalate, such as Dermol 105, neopentanoic acid isotridecyl ester, neopentanoic acid isooctadecane Base ester, Elefac I 205, isononoate, such as isononyl isononanoate, isononanoic acid isotridecyl ester, isononanoic acid Monooctyl ester, hydroxylating ester, such as two iso stearyl ester of lactic acid iso stearyl ester and malic acid,

Polyol ester and pentaerythritol ester, such as dipentaerythritol tetrahydroxy-stearic acid ester/pentaerythritol tetraisostearate,

The ester of dimer diol and diacid dimer, as Nippon Fine Chemical companies sell and describe in patent Shen Lusplan DD-DA5 that please be in US 2004-175 338^®With Lusplan DD-DA7^®,

The copolymer and its ester of polyalcohol and diacid dimer, such as Hailuscent ISDA or dilinoleic acid/butanediol copolymerization Object,

It is the fatty alcohol of liquid under room temperature (25 DEG C), there is branch containing 12 to 26 carbon atoms and/or unsaturated carbon-based Chain, such as 2- octyldodecanols, stearyl alcohol, isooctadecanol, cetanol, oleyl alcohol, 2- hexyl decyl alcohols, 2- butyl octanol and 2- ten One alkyl pentadecanol；

- C₁₂-C₂₂Higher fatty acids, such as oleic acid, linoleic acid or leukotrienes and its mixture,

Dialkyl carbonate, this 2 alkyl chains can be identical or different, if Cognis is with Cetiol CC^®It runs after fame the carbon of sale Dioctyl phthalate,

Have high molecular weight, especially have about 400 to about 10 000 g/mol, especially from about 650 to about 10 000 g/mol, especially from about 750 to about 7500 g/mol, particularly mole of about 1000 to about 5000 g/mol The oil of quality.As the oil for use in the present invention with high molecular weight, can especially mention selected from following oil：

Lipophilic polymers,

Straight-chain fatty acid ester with 35 to 70 total carbon number,

Hydroxylating ester,

Aromatic ester,

C₂₄-C₂₈Branched chain fatty acid or aliphatic alcohol ester,

Silicone oil,

The oil of plant origin, and

Their mixture；

Optional part alkyl and/or organosilicon fluorocarbon oil, for example, fluorosilicon oil described in document EP-A-847 752, perfluoroalkyl polyether and Fluorosilicone,

Silicone oil, such as line style or cyclic annular non-volatile dimethyl silicone polymer（PDMS）；Included in the side or end of organosilicon chain The alkyl at end, the dimethyl silicone polymer of alkoxy or phenyl, these groups contain 2 to 24 carbon atoms；Phenyl organosilicon, example Such as phenyl trimethicone, phenyl dimethicones, phenyl trimethicone siloxy diphenyl siloxane, hexichol Base dimethyl silicone polymer, diphenyl methyl diphenyl trisiloxanes and 2- phenylethyl trimethylsiloxysilicates, With

Their mixture.

(emulsifier)

In another embodiment, composition according to the present invention may include (d) at least one emulsifier.It can be applied in combination Two or more emulsifiers.Therefore, it is possible to use the combination of the emulsifier of single type or different types of emulsifier.

(d) emulsifier can be selected from nonionic emulsifier, anion emulsifier, amphoteric emulsifier, amphoteric ion emulsifier, Cationic emulsifier and its mixture.The example of emulsifier further includes natural or synthetic polymeric emulsifiers.

Anion emulsifier includes alkyl and alkyl ether sulfate, alkylsulfonate, alkyl and alkyl ether phosphate, alkyl Or alkyl ether sulfo succinate, alkyl and alkyl ether carboxy acid salt, wherein the alkyl include 8 to 30 carbon atoms, preferably 10 to The anionic derivative of 22 carbon atoms and alkyl polyglycoside, such as the citrate, tartrate or sulphur of alkyl polyglucoside Base succinate.

Nonionic emulsifier can broad definition be the compound containing hydrophobic part and nonionic hydrophile moiety.Hydrophobic part Example can be alkyl, alkyl aromatic and aryl aromatic fractions.The example of hydrophilic segment is polyoxyalkylene, amine oxide and alkane Alkylolamides.The example of nonionic emulsifier is alkoxy fatty alcohols or aliphatic acid, alkoxylate two-and three-styryls （stiryl）Phenol, polyhydroxy fatty acid amide, sugar ester and polyester, alkoxylated sugar esters, sorbitan and alkoxylate sorb Sugar alcohol acid anhydride aliphatic ester.Other examples of nonionic emulsifier include alkyl polyglycoside, such as cocounut oil poly glucoside.

Cationic emulsifier for use in the present invention contains amino or quaternary ammonium parent positively charged when dissolved in water Water section.The example of ammonium compounds is chain alkyl trimethyl ammonium chloride, chain alkyl benzyl chloride, alkylamine salt Hydrochlorate, alkylamine acetate and two (chain alkyl) ditallowdimethyl ammonium bromides.

Amphoteric emulsifier for use in the present invention can be can be by the wide in range derivative for being described as fatty quaternary ammonium compounds Those, wherein one of aliphatic substituent group contains anionic water solubilizing group, such as carboxylate radical, sulfonate radical, sulfate radical.Amphoteric surface The example of activating agent includes cocounut oil acyl both sexes base carboxyl propionate, cocoamphoacetate salt, cocounut oil acyl both sexes base oxalic acid Salt, Sodium Lauroamphoacetate.

The example of amphoteric ion emulsifier includes alkyl betaine and amido betaines, alkyl sulfo betaines, alkyl Glycinate and alkyl carboxyl glycinate.

Polymeric emulsifiers include but not limited to carboxylic acid polyalcohol, are containing one or more derived from propylene acid, substitution The cross-linking compounds of the monomer of the salt and derivative of acrylic acid and these acrylic acid and substitutional crylic acid.These carboxylic acid polyalcohols Serve as thickener.They can be the cross-linked homopolymer of acrylic acid or derivatives thereof such as acrylamidopropyl sulfonic acid.They Can be that there is (i) to be selected from (methyl) acrylic acid, its derivative, short chain（That is C₁-C₄）Acrylate monomer and its mixture First monomer；(ii) long-chain（That is C₈-C₄₀）Replace the copolymerzation with cross-linking of the second comonomer of polyethylene glycol acrylate monomeric form Object.

The example of available commercially available carboxylic acid polyalcohol is Carbopol 1342, Pemulen TR-1 or TR-2 herein （INCI:Acrylate/acrylic acid C10-30 alkyl ester cross-linked polymers comes from Lubrizol Corp.）；Sepigel 305、 Simulgel EG、Simulgel NS、Simulgel 600（From Seppic S.A.）；Viscolam AT100P and Viscofam AT64/P（From Lamberti S.p.A.）.

The other materials for being suitable as polymeric emulsifiers include ethylene oxide/propylene oxide block copolymer, such as with quotient Those of name of an article Pluronic (BASF) sales.

Other suitable polymeric emulsifiers include natural polymer derivative, the polysaccharide of such as available hydrophobic part derivatization. The further example of the suitable emulsifying agent of composition for use in the present invention is disclosed in " McCutcheon's Detergents and Emulsifiers", North American Edition (2003), Allured Publishing In Corporation.

(d) emulsifier is preferably selected from polymeric emulsifiers, is more preferably selected from association polymer, is even more preferably selected from acrylic acid Ester/acrylic acid C10-30 alkyl ester cross-linked polymers, such as Pemulen TR2.

(d) amount of the emulsifier in composition according to the present invention can be 0.01 to 15 weight of the composition total weight Measure %, preferably 0.05 to 10 weight %, more preferable 0.1 to 5 weight %.

[composition]

Composition according to the present invention is intended as cosmetic composition.Therefore, cosmetic composition according to the present invention is intended to It is applied on keratin substances.Keratin substances refer to the material as main element, example packet herein containing keratin Include skin, scalp, nail, lip, hair etc..Therefore, cosmetic composition according to the present invention is preferred for keratin substances, The especially beauty method of skin.

Therefore, cosmetic composition according to the present invention can be skin cosmetic composition, preferably skin care compositions or Skin make-up composition, the composition for the pollutant for especially being used to that skin to be protected to resist in ultraviolet light and/or air.

Composition according to the present invention can be any form, such as solution, dispersion, lotion, gel and cream.If according to The composition of the present invention includes (c) at least one oil, and composition according to the present invention can be lotion, such as W/O, O/W, W/O/W And O/W/O, the preferred form of O/W lotions.

Composition according to the present invention can be by according to well known to a person skilled in the art any methods to mix above-mentioned necessity It is prepared with optional member.

[film]

Composition according to the present invention can be used for easily preparing relatively thick film.

Therefore, it is prepared the invention further relates to a kind of with being more than 1 μm, preferably 1.5 μm or bigger, more preferable 2 μm or more The film of big thickness, the preferably method of cosmetics film, the method includes：

Apply composition according to the present invention in substrate, preferably keratin substrate, more preferable skin；With

The composition is dried.

The upper limit of the thickness of film according to the present invention is unrestricted.Thus, for example, the thickness of film according to the present invention can be with For 1 mm or smaller, preferably 500 μm or smaller, more preferable 300 μm or smaller, even more preferably 100 μm or smaller.

Since the method according to the present invention for preparing film includes that composition according to the present invention is applied to substrate, preferred angle Albumen substrate, the step dried on more preferable skin and by the composition, do not need according to the method for the present invention any spin coating or Spraying, therefore can easily prepare relatively thick film.Therefore, the method according to the present invention for preparing film can not have to any Special installation, as spin coater and flush coater can prepare relatively thick film.

It is still thin and possible transparent, it is thus possible to be not easy to examine although film according to the present invention is relatively thick Feel.Therefore, film according to the present invention is preferably used as cosmetics film.

If the substrate is not keratin substrate such as skin, composition according to the present invention can be applied to by non-angle egg In the substrate that white any material is constituted.The material of non-keratin substrate is unrestricted.Two or more can be applied in combination Material.Therefore, it is possible to use the combination of the material of single type or different types of material.Under any circumstance, the substrate is excellent Choosing is flexible（flexible）Or elasticity.

If the substrate is not keratin substrate, the substrate is preferably water-soluble, because can be by the way that base is washed with water Bottom and leave film according to the present invention.As the example of water-soluble material, can mention poly- (methyl) acrylic acid, polyethylene glycol, Polyacrylamide, polyvinyl alcohol（PVA）, starch, cellulose acetate etc..PVA is preferred.

If the non-keratin substrate is sheet-form, thickness can be more than film according to the present invention, with easy to operate attached The film on base sheet.The thickness of the non-keratin base sheet is unrestricted, but can be 1 μm to 5 mm, preferably 10 μm to 1 mm, more preferable 50 to 500 μm.

Film according to the present invention can be more preferably detached from from non-keratin substrate.Disengaging pattern is unrestricted.Therefore, according to The film of the present invention can be removed from non-keratin substrate, or be detached from by base sheet is dissolved into solvent such as water.

The invention further relates to：

The composition is dried,

With

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values.

Above-mentioned explanation be applicable to it is above-mentioned cation and anionic polymer and it is above-mentioned have two or more pKa values Non-polymeric acid or its salt.

Thus obtained film can be supported oneself above.Term " is supported oneself（self-standing）" refer to that the film can herein To be sheet-form and can be operated as separate sheet in the case where no substrate or carrier are assisted.Therefore, term " oneself It is vertical " can have and " self-supporting（self-supporting）" identical meaning.

Film according to the present invention is preferably hydrophobic.

Term " hydrophobic " refers to the polymer herein at 20 to 40 DEG C, at preferably 25 to 40 DEG C, more preferable 30 to 40 DEG C Water（It is preferred that having 1 liter of volume）In solubility be the polymer total weight be less than 10 weight %, preferably smaller than 5 weight %, More preferably less than 1 weight % is even more preferably less than 0.1 weight %.The polymer is most preferably not soluble in water.

If film according to the present invention is hydrophobic, the film can have water-fast property, therefore even if keratin substrate table Face is got wet due to such as sweat and rainwater, which can also stay on keratin substrate such as skin.Therefore, if according to the present invention Film any cosmetic result can be provided, which can be long lasting for.

On the other hand, film according to the present invention is easy under alkaline condition, such as 8 to 12, preferably 9 to 11 pH from keratin It is removed on substrate such as skin.Therefore, film according to the present invention is difficult to be removed with water, and it is easy the alkaline item as it can provide The soap of part removes.

Film according to the present invention may include at least one bio-compatible and/or Biodegradable polymeric layer.It can group It closes and uses two or more bio-compatibles and/or Biodegradable polymeric.Therefore, it is possible to use the biology of single type The combination of compatible and/or Biodegradable polymeric or different types of bio-compatible and/or Biodegradable polymeric.

Term " bio-compatible " polymer refers to that the polymer does not include skin in polymer and live body in the present specification Excessive interaction between cell in skin, and the polymer will not be considered as exotic by live body.

Term " biodegradable " polymer refers to that the polymer can be due to the generation of such as live body itself in the present specification It thanks or is likely to be present in the metabolism of the microorganism in live body and degrade or decompose in the living body.The biodegradable polymer also may be used Pass through hydrolytic degradation.

If film according to the present invention includes bio-compatible and/or Biodegradable polymeric, to skin irritatin compared with It is low or non-stimulated, and any measles are not caused.Further, since using bio-compatible and/or Biodegradable polymeric, root According to the cosmetics film of the present invention（cosmetic sheet）Can it is well attached on the skin.

Film according to the present invention can be used for the cosmetic treatments of keratin substances, preferably skin, especially face.According to the present invention Film can be any shape or form.For example, it can be used as the part of full face diaphragm or face, such as cheek, nose and eye The patch in week.

[beauty method and purposes]

The invention further relates to：

Keratin substrate, such as the beauty method of skin comprising；Apply the composition of the present invention in keratin substrate；And it will The composition drying in keratin substrate to form cosmetics film；With

Composition according to the present invention is used to prepare the purposes of cosmetics film in keratin substrate such as skin.

Beauty method refers to beautiful for the nursing on the surface of keratin substrate such as skin and/or the non-therapeutic of makeup herein Appearance method.

In the above method and on the way, above-mentioned cosmetics film is resistant to pH 7 or smaller water, and available pH is more than 7, preferably 8 Or bigger, more preferable 9 or bigger water remove.

In other words, above-mentioned cosmetics film is in neutral or acid condition, such as 7 or smaller, and preferably 6 or bigger and 7 or smaller, more It is preferred that water-fast under 5 or bigger and 7 or smaller pH, and above-mentioned cosmetics film is in alkaline condition, such as larger than 7, preferably 8 or bigger, More preferable 9 or bigger pH under can remove.The pH upper limits are preferably 13, and more preferable 12, even more preferably 11.

Correspondingly, above-mentioned cosmetics film can be water-fast, therefore even if the surface of keratin substrate due to such as sweat and rainwater And get wet, which can also stay on keratin substrate such as skin.On the other hand, above-mentioned cosmetics film can be easy under alkaline condition Ground is removed from keratin substrate such as skin.Therefore, film according to the present invention is difficult to be removed with water, and it can be easily with can carry It is removed for the soap of alkaline condition.

Due to the property of the poly ion complexes particle in the cosmetics film, even if the cosmetics film does not include any makeup Product active constituent, above-mentioned cosmetics film can also have cosmetic result, such as absorb or adsorb stink, change keratin substrate such as skin Appearance, change keratin substrate sense of touch and/or protection keratin substrate resist such as dust or pollutant.

In addition, above-mentioned cosmetics film can immediately be changed by changing light reflection on skin etc. or modification skin appearance, i.e., It includes any cosmetic active ingredient to make the cosmetics film not.Therefore, above-mentioned cosmetics film is possible to cover skin blemishes, such as hair Hole or wrinkle.In addition, above-mentioned cosmetics film can immediately be changed by changing surface roughness on skin etc. or modification skin touches Sense.In addition, above-mentioned cosmetics film can such as be polluted by covering skin surface and being used as barrier protection skin from environmental stress Object, impurity etc. protect skin immediately.

On can adjusting or control by changing chemical composition, thickness and/or the surface roughness of above-mentioned cosmetics film State cosmetic result.

If above-mentioned cosmetics film includes at least one cosmetic active ingredient, which can have by the makeup The cosmetic result that product active constituent provides.For example, if the cosmetics film include selected from age resister, anti-sebum agent, deodorant, At least one cosmetic active ingredient of antiperspirant, brightening agent and its mixture, the cosmetics film can handle skin aging, absorb Sebum on skin, the smell on control skin, the perspiration on control skin and/or skin whitening.

For example, if the cosmetics film includes ultraviolet filtering agent, above-mentioned cosmetics film can limit skin darkening, improve The colour of skin and colour of skin uniformity, and/or processing skin aging.

After being applied on skin, color make-up composition can also be applied to cosmetics film according to the present invention （cosmetic sheet）On.

Embodiment

By embodiment the present invention will be described in more detailed manner.But they are not necessarily to be construed as the limitation present invention Range.

[preparation of poly ion complexes particle]

(embodiment 1)

15.0 grams of carboxymethyl cellulose（CMC）5 weight % aqueous solutions and 10.0 grams of polylysine（Plys）5 weight % water Solution（pH 6.1）It is mixed using propeller mixer（700rpm 20min）, and will thus be obtained by adding 1.8 grams of NaOH The pH of the mixture obtained is adjusted to 10.8.While agitating, contain 33 weight % Terephthalidene Dicamphor Sulfonic Acids by 2 grams （Mexoryl SX）Aqueous solution be added in said mixture.With thus obtained mixture pH reduce, formation gather from Sub- compound gel particles（PGP）, while Mexoryl SX are trapped in PGP.Therefore, stable PGP dispersions are successfully prepared Body.The final pH of the PGP dispersions is 7.7.The granularity of the PGP is about 3 μm.

It is used to prepare and is shown according to the material of the PGP dispersions of embodiment 1 and the property of thus obtained PGP dispersions In table 1.The numerical value of component amount shown in table 1 is all based on " gram ".

(embodiment 2-5)

It repeat according to the program of embodiment 1, condition to be prepared according to the PGP of embodiment 2-5 points using material shown in table 1 Granular media.

In example 4, Yellow 6 uses cation exchange resin first（Diaion SK1B, Mitsubishi Chemical）Processing using by the sodium ion exchange of Yellow 6 as hydrogen ion.The pH of the 30 weight % solution of Yellow 6 used It is 2.6.

Table 1

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						CMC (5 weight % solution)	15.0	-	15.0	-	15.0
CMC (10 weight % solution)	-	13.8	-	13.8	-
						Plys (Everguard PL) (5 weight % solution, pH 6.1)	10.0	-	10.0	-	10.0
Plys (Everguard PL) (10 weight % solution, pH 11 is adjusted to by NaOH)	-	23.7	-	23.7	-
						Mexoryl SX (33 weight % solution)	2.0	10.5	-	-	1.0
Ascorbic acid solution (10 weight %, pH 2.2)	-	-	5.7	-	-
						6 solution of Yellow (30 weight %, pH 2.6) (being handled with cation exchange resin)	-	-	-	10.0	-
NaOH	1.8	-	1.8	-	1.8
						1N HCl	-	-	-	-	2.0
H₂O	71.2	52.0	67.5	52.5	70.2
						It amounts to	100.0	100.0	100.0	100.0	100.0
Granularity (μm)	About 3	About 10	About 10	About 20	About 5
						pH	7.7	6.9	6.8	6.7	4.8
Stability	Stablize	Stablize	Stablize	Stablize	Stablize

Mexoryl SX:

Yellow 6:

。

Stablized at room temperature 2 weeks according to all PGP dispersions of embodiment 1-5.Therefore, do not had visually up to 2 weeks Observe sediment.

[preparation and assessment of the film made of PGP]

(water resistance and available soap scavenging)

By using 30 microlitres of PGP dispersions according to embodiment 2, in polymethyl methacrylate（PMMA）Plate （HELIOPLATE HD6）Rough surface on written word female " G " and be dried at room temperature for.It prepares and contains on PMMA plates The film made of PGP of letter " G " form of Mexoryl SX.

By using UV lamp from the front illuminated ultraviolet light of PMMA plates, on the front of PMMA plates visible dark alphabetical " G ". Consequently found that including the above-mentioned film of Mexoryl SX（Hereinafter referred to as " PGP films "）With UV shield effectiveness.

With the originally water washing of flowing after five minutes, then from the back side illuminaton ultraviolet light of PMMA plates.Dark letter " G " is still It stays on PMMA plates.Consequently found that above-mentioned PGP films still have UV shield effectiveness.

In order to check the erasability of PGP films, by commercial soap liquid product（pH 10.5）It is placed on PGP films, retains on it 10 seconds, flowing water washing is used in combination 10 seconds.Again from the front illuminated ultraviolet light of PMMA plates.Alphabetical " G " is no longer stayed on PMMA plates.Cause This finds the pH dependences of erasability or solubility due to the PGP films, washes off above-mentioned PGP films completely with soap.This PGP body System is that the charge density of the polylysine in the PGP systems is reduced in pH 10.5 with the reason of pH pauper characters（pKa: About 9）, and polylysine dissociates（Last PGP films disappear）.

(external spf value)

In order to manufacture the PGP films of the SX containing Mexoryl, in PMMA plates（HELIOPLATE HD6）Rough surface on apply it is 100 micro- It rises the PGP dispersions according to embodiment 2 and is dried at room temperature for.It is prepared on transparent PMMA plates and contains the transparent of Mexoryl SX PGP films.

The external spf value of PGP films is measured with SPF analyzers UV-2000S.The measurement of external spf value carries out twice：With Before water washing PGP films and after washing PGP films.

The washing procedure is as follows：5 milliliters of water are placed on PMMA plates.After impregnating 1 minute in water, 300 millis of the PGP films Up-flow moves pure water washing.Finally, the PGP films commercial soap liquid product（pH 10.5）Washing.That is, soap product is set In on PGP films, retain 10 seconds on it, flowing originally water washing is used in combination.External spf value is shown in table 2.

Table 2

	Before being washed with water	After washing with water	With after soaping and washing
				External SPF	105	53	1

The PGP films show high external spf value before being washed with water, and even also keep its UV screen after washing with water Cover effect.On the other hand, which is easy to be washed off with basic soap, and generates extremely low external spf value.

[scanning electron microscope (SEM) measurement]

Pass through the structure of sem analysis PGP films（Cross-sectional analysis）.

Prepare sample as follows：50 microlitres are applied on a glass according to the PGP dispersions of embodiment 2 and is done at room temperature It is dry to form PGP films.It is coated with osmium on the surface of PGP films（Hollow cathode plasma CVD）To prepare sample.The sample is embedding In acrylic resin（acryl resin）In.Use ion polishing（Ilion+）And the sources Ar, prepare cross section table with cooling method Face.Machine：Sem analysis（Hitachi Hightechnologies, S-4800）, EDX analysis（EDAX Genesis2000）.

It is that the SEM of cross section as PGP films is measured as a result, finding that PGP merges the domain for forming bigger in the drying process. Some PGP not yet merge the domain for forming bigger.

As SEM-EDX analyses as a result, finding that Mexoryl SX molecules exist only in the domain of PGP and bigger.

Then, the PGP films are washed with water.Result as SEM-EDX analyses, it was found that, although being washed with water, merging The domains PGP generate uniform continuous film.In addition, Mexoryl SX are evenly distributed in the film.

[O/W lotions]

(embodiment 6 and 7)

By using acrylate/acrylic acid C10-30 alkyl ester cross-linked polymers（Pemulen TR-2）And methoxy cinnamic acid Ethylhexyl（MCX）, preparation includes the stabilization O/W lotions of PGP.

First, PGP dispersions are prepared by method same as Example 1, condition is using material system shown in table 3 The standby PGP dispersions.

Then, Pemulen TR-2 and MCX is added into the PGP dispersions and is emulsified using homogenizer（7000 rpm and 20 minutes）（Embodiment 6）.Success preparation includes the stabilization O/W lotions of PGP.In order to improve external SPF and water resistance, implementing Also increase Mexoryl SX and polyquaternium -6 in example 7（Polycation）Amount.

It is used to prepare and is shown according to the material of the O/W lotions of embodiment 6 and 7 and the property of thus obtained O/W lotions In table 3.The numerical value of component amount shown in table 3 is all based on " gram ".

Table 3

	Embodiment 6	Embodiment 7
			CMC (10 weight % solution)	24.8	24.8
Plys (PL-25) (25 weight % solution, pH 10.6)	11.4	11.4
			Mexoryl SX (22 weight % aqueous solutions)	30.0	-
Mexoryl SX (33 weight % aqueous solutions)	-	30.0
			Sodium styrene/MA^*Copolymer (40 weight % solution)	0.7	0.7
Polyquaternium -6 (40 weight % solution)	5.3	6.9
			NaOH	1.0	1.0
Phenoxetol	0.5	0.5
			H₂O	18.7	17.1
Acrylate/acrylic acid C10-30 alkyl ester cross-linked polymers (Pemulen TR-2)	0.1	0.1
			MCX	7.5	7.5
It amounts to	100	100
			pH	4.8	5.0
Stability	Stablize	Stablize

MA:Maleic acid.

All stablized at room temperature 2 weeks according to the O/W lotions of embodiment 6 and 7.Therefore, it was not observed visually up to 2 weeks To sediment.

By by polymeric emulsifiers（Pemulen TR-2）With oil-soluble UV line filtering agent（MCX）It is added to PGP dispersions In body, stable O/W lotions are prepared.

[assessment of O/W lotions]

(external SPF)

In PMMA plates（HELIOPLATE HD6）Rough surface on apply 30 milligrams according to the O/W lotions of embodiment 6 and in room The lower drying of temperature.The hyaline membrane containing MCX and Pemulen TR-2 is prepared on PMMA plates.

The external spf value of above-mentioned film is measured with SPF analyzers UV-2000S.The measurement of external spf value carries out twice：With Before the water washing film and after the film is washed with water.

It is as follows that program is washed with water in this：5 milliliters of water are placed on PMMA plates.After impregnating 1 minute in water, the film is with 300 Milliliter flows pure water washing.The external spf value of each film made of the O/W lotions according to embodiment 6 and 7 is shown in table 4.

Then, water resistance is defined as：

(the external SPF before being washed with water)/(the external SPF after being washed with water) x 100 (%).

The water resistance of each film made of the O/W lotions according to embodiment 6 and 7 is shown in table 4.

With commercial soap liquid product（pH 10.5）Above-mentioned external spf value is measured again after washing the film.

This is as follows with soap washing procedure：By 5 milliliters of commercial soap products（pH 10.5）It is placed on PMMA plates.It is produced in the soap lye After being impregnated 1 minute in product, 300 milliliters of pure water washings of flowing of the film.It is each made of the O/W lotions according to embodiment 6 and 7 The external spf value of film is shown in table 4.

Table 4

	Embodiment 6	Embodiment 7
			External SPF before washing	53	134
External SPF after washing	40	115
			Water resistance (%)	75	86
External SPF after being washed with soap (pH 10.5)	2	3

Go out high external spf value according to the O/W emulsions displays including PGP of embodiment 6 and 7.Even if after washing with water, They also keep high external spf value（Water resistance：75% and 86%）.By increasing Mexoryl SX and polyquaternium -6（Poly- sun Ion）Amount, improve external spf value and water resistance.In addition, being easy by the film obtained according to the O/W lotions of embodiment 6 and 7 It is washed off with basic soap liquid product as mentioned above.

[scanning electron microscope (SEM) measurement]

It include the structure of the film of Mexoryl SX and MCX and Pemulen TR-2 by sem analysis（Cross-sectional analysis）.

Prepare sample as follows：By 30 microlitres there is the O/W lotions of the formula shown in the following table 5 according to embodiment 8 to apply In PMMA plates（HELIOPLATE HD6）Plane on and be dried at room temperature for form film.It is coated with osmium on the surface of the film （Hollow cathode plasma CVD）To prepare sample.By the sample in acrylic resin.Use ion polishing（Ilion +）And the sources Ar, prepare cross-sectional surface with cooling method.Machine：Sem analysis（Hitachi Hightechnologies, S- 4800）, EDX analysis（EDAX Genesis2000）.The numerical value of component amount shown in table 5 is all based on " gram ".

Table 5

	Embodiment 8
		CMC (10 weight % solution)	24.8
Plys (PL-25) (25 weight % solution, pH 10.6)	17.08
		Mexoryl SX (22 weight % aqueous solutions)	40.0
Sodium styrene/MA^*Copolymer (40 weight % solution)	0.7
		Polyquaternium -6 (40 weight % solution)	1.18
Pemulen TR-2	0.2
		MCX	7.5
Mexoryl XL	3.0
		NaOH	1.86
H₂O	3.68
		It amounts to	100
pH	5.1
		Stability	Stablize

MA:Maleic acid.

It is that the SEM of cross section as above-mentioned film is measured as a result, find that the surface of the film is smooth and include MCX and Mexoryl XL（Hydrophobic ultraviolet filtering agent）.All PGP merge to form uniform films.

As SEM-EDX analyses as a result, finding that Mexoryl SX and Mexoryl XL molecules exist only in above-mentioned film. It has also been found that Mexoryl SX are evenly distributed in the film, and Mexoryl XL are mainly distributed near the surface of film.

Therefore, the film based on embodiment 8 can express out high external spf value.

[adsorption/absorption of stink]

For deodorant/antiperspirant purposes, PGP is measured to isovaleric acid（IVA）（It is one of the main malodor molecules in sweat） Adsorption capacity.

140 microlitres of PGP dispersions according to embodiment 2 are deposited on filter paper and are dried.Then, by the 0.04 of 20 microlitres Wt% IVA standard aqueous solutions are placed on the filter paper and the filter paper are placed in bottle.PGP films on the filter paper and between IVA Reaction carried out 30 minutes at 40 DEG C.The IVA concentration in detection bottle head space is analyzed by GC/MS, and calculates IVA's as follows It reduces：

Reduce (%)={ (A-B)/A } X100

A:IVA concentration in standard solution,

B:There are IVA concentration when PGP

As a result:The head space IVA that PGP films show 90% is reduced.These are the result shows that PGP has good stink adsorption/absorption Ability simultaneously can be used for deodorant/antiperspirant purposes.

[anti-fouling effect]

In order to assess the anti-fouling effect of PGP films, the PGP dispersions according to embodiment 9 shown in the following table 6 are deposited to 20 minutes are dried in bioskin substrates and at 35 DEG C to form PGP films in bioskin substrates.Component amount shown in table 6 Numerical value be all based on " gram ".

Using iron oxide particles as the model of dirt.It is sieved with 2 mg/cm via 150 um²Amount iron oxide particles are small On the PGP films that the heart is spread in bioskin substrates and on the surface of the bioskin substrates that are spread to no PGP films.Then, in order to assess Antifouling or anti-attachment effect blows the iron oxide particles mainly deposited by gravitational effect off by soft air.Hereafter, by aobvious Micro mirror observes surface of the tool with/without the bioskin substrates of PGP films under 5x magnifying powers.On PGP films in bioskin substrates Iron oxide particles amount significantly lower than the iron oxide particles amount in the bioskin substrates of no PGP films.

Table 6

	Embodiment 9
		CMC (10 weight % solution)	24.8
Plys (PL-25) (25 weight % solution, pH 10.6)	14.23
		Mexoryl SX (22 weight % aqueous solutions)	40.0
SMA (40 weight % solution)	0.7
		Polyquaternium -6 (40 weight % solution)	1.18
H₂O	13.57
		NaOH	0.52
Glycerine	5
		It amounts to	100.00
pH	6.03
		Stability	Stablize

[comparative study]

(comparative example 1)

Instead of the Meroxyl SX in embodiment 1, using HCl as acid.

5 weight % aqueous solutions of the 5 weight % aqueous solutions and 10.0 grams of Plys of the CMC of 15.0 grams of mixing, and pass through 1.8 grams The pH of the mixture is adjusted to 10.8 by NaOH.While agitating, 2 grams of 1N HCl aqueous solutions are added to said mixture In.In comparative example 1, stable PGP dispersions can not be prepared, and observe some sediments within 2 weeks at room temperature.

It is used to prepare and is shown according to the material of the PGP dispersions of comparative example 1 and the property of thus obtained PGP dispersions In table 7.The numerical value of component amount shown in table 7 is all based on " gram ".

(comparative example 2)

Instead of the Meroxyl SX in embodiment 1, use (+) -10- camphorsulfonic acids as acid.

5 weight % aqueous solutions of the 5 weight % aqueous solutions and 10.0 grams of Plys of the CMC of 15.0 grams of mixing, and pass through 1.8 grams The pH of the mixture is adjusted to 10.8 by NaOH.Under agitation, 33 weight % of 2 grams of (+) -10- camphorsulfonic acids are water-soluble Liquid is added in said mixture.In comparative example 2, stable PGP dispersions can not be prepared, and at room temperature within 2 weeks Observe big sediment.

It is used to prepare and is shown according to the material of the PGP dispersions of comparative example 2 and the property of thus obtained PGP dispersions In table 7.The numerical value of component amount shown in table 7 is all based on " gram ".

Table 7

	Comparative example 1	Comparative example 2
			CMC (5 weight % solution, pH6)	15.0	15.0
Plys (Everguard PL) (5 weight % solution, pH 6.1)	10.0	10.0
			NaOH	1.8	1.8
1N HCl	2.5	-
			(+) -10- camphorsulfonic acids (33 weight % solution)	-	4.0
H₂O	70.7	69.2
			It amounts to	100.0	100.0
Appearance	Sediment	Sediment
			pH	7.5	6.9
Stability	Sediment	Sediment

(+) -10- camphorsulfonic acids：

。

Comparative example 1 and 2 shows PGP dispersions can not be made steady using the inorganic monovalent or organic acid with only one pKa value It is fixed.

Claims

1. composition, it includes：

(a) at least one particle, the particle include

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values；With

(b) at least one physiologically acceptable volatile media.

2. composition according to claim 1, wherein the charge density of the cationic polymer is 0.1 meq/g to 20 Meq/g, preferably 1 to 15 meq/g, more preferable 4 to 10 meq/g.

3. according to the composition of claims 1 or 2, wherein the cationic polymer is selected from secondary or tertiary ammonia at least one Base, quaternary ammonium group, guanidine radicals, biguanides base, imidazole radicals, imino group, the positively chargeable of pyridyl group and amino and/or positively charged Part.

4. according to the composition of any one of claims 1 to 3, wherein the cationic polymer is selected from cyclopolymers of alkyldiallylamine The cyclopolymer of cyclopolymer and dialkyl diallyl ammonium, such as (total) polydiene propyl dialkylammonium chloride, it is (total) poly- Amine, such as (total) polylysine, cationic (total) polyaminoacid, such as collagen and its salt.

5. according to the composition of any one of Claims 1-4, wherein if the anionic polymer is synthetic anionic polymerization Object, the charge density of the anionic polymer be 0.1 meq/g to 20 meq/g, preferably 1 to 15 meq/g, more preferable 4 to 10 meq/g, and if the anionic polymer is natural anionic polymer, the average substitution of the anionic polymer Degree is 0.1 to 3.0, preferably 0.2 to 2.7, more preferable 0.3 to 2.5.

6. according to the composition of any one of claim 1 to 5, wherein the anionic polymer is selected from sulfuric acid at least one Base, sulfate radical, sulfonic group, sulfonate radical, phosphate, phosphate radical, phosphonic acid base, phosphonate radical, carboxylic acid group and carboxylate radical can be negatively charged Lotus and/or negatively charged part.

7. according to the composition of any one of claim 1 to 6, wherein the anionic polymer is selected from polysaccharide, such as alginic acid, transparent Matter acid and cellulosic polymer（Such as hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, ethylhydroxyethylcellulose And carboxymethyl cellulose）, anion (total) polyaminoacid such as (total) polyglutamic acid, (total) poly- (methyl) acrylic acid, (total) polyamides Amino acid, (total) poly styrene sulfonate, (total) poly- (oxyethylene sulfate), dextran sulfate, chondroitin sulfate, (total) poly- Malaysia Acid, (total) poly- fumaric acid, maleic anhydride (co) polymer and its salt.

8. composition according to any one of claims 1 to 7, the wherein ratio of the amount of cationic polymer/anionic polymer For 0.05-18, preferably 0.1-10, more preferable 0.5-5.0.

9. according to the composition of any one of claim 1 to 8, wherein cationic polymer or anionic polymerisation in the composition Object or 0.01 to the 20 weight % that the amount of cation and anionic polymer is the composition total weight, preferably 0.1 to 15 weight Measure %, more preferable 0.3 to 12 weight %.

10. according to the composition of any one of claim 1 to 9, wherein the non-polymeric acid with two or more pKa values Or its salt is organic acid or its salt, preferably hydrophilic or water-soluble organic acid or its salt.

11. composition according to any of claims 1 to 10, wherein described non-polymeric with two or more pKa values Acid is non-polymeric polybasic acids.

12. according to the composition of any one of claim 1 to 11, wherein described non-polymeric with two or more pKa values Acid has at least two acidic groups selected from carboxylic acid group, sulfate, sulfonic group, phosphonic acid base, phenolic hydroxyl and its mixture.

13. according to the composition of any one of claim 1 to 12, wherein described non-polymeric with two or more pKa values Acid or its salt are selected from Terephthalidene Dicamphor Sulfonic Acid and its salt（Mexoryl SX）、Yellow 6（Sunset Yellow FCF）, ascorbic acid and its salt and its mixture.

14. according to the composition of any one of claim 1 to 13, wherein described non-polymeric with two or more pKa values The amount of acid or its salt in the composition is 0.001 to 30 weight % of the composition total weight, preferably 0.01 to 20 weight Measure %, more preferable 0.1 to 15 weight %.

15. according to the composition of any one of claim 1 to 14, wherein the size of (a) particle is 50 nm to 100 μm, preferably 200 nm to 50 μm, more preferable 300 nm to 30 μm.

16. according to the composition of any one of claim 1 to 15, wherein the amount of (a) particle in the composition is described group Close 0.01 to the 60 weight %, preferably 0.1 to 50 weight %, more preferable 1 to 40 weight % of object total weight.

17. according to the composition of any one of claim 1 to 16, wherein (b) at least one physiologically acceptable volatile media, It is preferred that water, amount in the composition is 50 to 99 weight % of the composition total weight, preferably 60 to 97 weight %, more excellent Select 70 to 95 weight %.

18. according to the composition of any one of claim 1 to 17, wherein the pH of the composition is 3 to 9, preferably 3.5 to 8.5, More preferable 4 to 8.

19. according to the composition of any one of claim 1 to 18, wherein the composition further includes (c) at least one oil And it is emulsion form.

20. composition according to claim 19, wherein the composition further includes (d) at least one emulsifier, preferably Polymeric emulsifiers.

21. according to the composition of any one of claim 1 to 20, wherein the composition is cosmetic composition, preferred skin Cosmetic composition.

It is more than 1 μm, preferably 1.5 μm or bigger 22. preparing and having, the film of the thickness of more preferable 2 μm or bigger is preferably made up The method of product film, the method includes：

Apply the composition according to any one of claim 1 to 21 in substrate, preferably in keratin substrate；With

The composition is dried.

23. with 1 μm, preferably 1.5 μm or bigger is more than, the film of the thickness of more preferable 2 μm or bigger, preferably cosmetics film, It is prepared by the method included the following steps：

The composition is dried.

24. with 1 μm, preferably 1.5 μm or bigger is more than, the film of the thickness of more preferable 2 μm or bigger, preferably cosmetics film, It includes：

At least one cationic polymer,

At least one anionic polymer, and

At least one non-polymeric acid or its salt with two or more pKa values.

25. the beauty method of keratin substrate such as skin comprising

Apply the composition according to any one of claim 1 to 21 in the keratin substrate；With

The composition is dried to form cosmetics film in the keratin substrate.

26. being used in keratin substrate according to the composition of any one of claim 1 to 21 as prepared cosmetics film on skin Purposes, wherein the cosmetics film be resistant to pH 7 or smaller water, and can with pH be more than 7, preferably 8 or bigger, more preferable 9 or The water of bigger removes.